CN103694746B - A kind of preparation method of multifunctional magnetic synthetic mica pearlescent pigment - Google Patents
A kind of preparation method of multifunctional magnetic synthetic mica pearlescent pigment Download PDFInfo
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Abstract
A preparation method for multifunctional magnetic synthetic mica pearlescent pigment, comprises the following steps: the synthesis of template, the preparation of matrix, prepare rare-earth oxide sulfate high-visibility pigment and Fe
3o
4namely multifunctional magnetic synthetic mica pearlescent pigment is obtained after coating, the present invention substitutes natural mica with synthetic mica, not containing heavy metal ion (as: cadmium, lead, mercury, sexavalent chrome etc.), synthesis technique utilize rare-earth oxide sulfate as promotor, instead of tin ion promotor in traditional technology and can give synthetic mica pearly pigment magnetic conduction function, be conducive to the shielding properties improving electromagnetic screen coating.And the intended application field of the product be suitable for is extensive, be specially adapted to the paint with electromagnetic shielding function such as electronic apparatus, mobile phone, and the weather-proof level decorative paint used in the severe environment such as car paint, exterior coating, the advantage show excellent weather resistance, combining decoration functions with electro-magnetic screen function.
Description
Technical field
The present invention relates to preparation method's technical field of pearly pigment, particularly relate to a kind of preparation method of multifunctional magnetic synthetic mica pearlescent pigment.
Background technology
Along with the application surface of pearly pigment is constantly widened, various specific function novel macreous pigments become the bright spot in market, and in order to meet the demand in market, the pearly pigment of all kinds of specific function also becomes the emphasis of development project.Magnetic conductive bead delustering pigment just belongs to one of specific function pearly pigment, the environment-friendly type magnetic conductive bead delustering pigment of production application in coating and to reduce hazardous and noxious substances in coating be the important development direction of current coating, natural mineral dye, often containing heavy metal, thus produces material impact to the feature of environmental protection of coating.Nacreous mica pigment, with the feature such as the chemical stability of its excellence, strong covering power, specific refractory power be high, colorful and nontoxic, is widely used in the industry such as coating, paint, ink, makeup, plastics, rubber and printing.The production of pearly pigment and application have catered to the mankind to beautiful and higher level to color pursuit, and therefore its research and producing all develops very fast.Usual employing chemical liquid deposition is coated prepares pearlescent mica pigment.Conventional coating has TiO
2, Fe
2o
3, Cr
2o
3deng; The mineral type of mica substrate has white mica and phlogopite.But Chinese natural mica reserves are few and many containing spot and impurity, quantitatively or qualitatively all can not satisfy the demand.For making up natural mica deficiency, comprise many manufacturers of Guangdong Volor Pearl Pigment Co., Ltd in recent years, develop and produced with the nacreous mica pigment product prepared by compound mica replacement natural mica powder, compared with natural mica pearly pigment, there is pure, high temperature resistant, good weatherability, the feature that whiteness is high.Take synthetic mica as the pearly pigment of raw material, not containing heavy metal ion (as: cadmium, lead, mercury, sexavalent chrome etc.), and in traditional pearly pigment the content of heavy metal ion lead generally at 12-16PPM.Therefore, synthetic mica can be used for preparing more high-grade pearly pigment.
The most frequently used coating of nacreous mica pigment is TiO
2, dominant has rutile-type and Detitanium-ore-type two kinds mutually.Because anatase octahedrite has stronger photochemical activity, through the irradiation of long-term natural light (containing ultraviolet), paint base is easily made to be oxidized, produce powder phenomenon-tion, and the chemical property of rutile is more stable, therefore, when synthetic mica pearly pigment, generally all wish to obtain rutile-type nacreous mica pigment.In normal circumstances, pure anatase titanium dioxide TiO
2change rutile TiO into
2temperature be 618-915 DEG C.Make anatase titanium dioxide TiO
2all change rutile TiO into
2, calcining temperature is to be advisable higher than 1000 DEG C.Realize TiO
2phase transformation thoroughly, needs higher Heating temperature and longer heat-up time usually, and temperature high like this can cause the structure of mica to suffer certain destruction on the one hand, and then causes the distortion of mica substrate and gloss to reduce; Also cause industrial production energy consumption large on the other hand, cost is high.For solving the problem, must find and reduce TiO
2the method of transformation temperature.Current majority report adopts to mix SnO
2promote TiO
2changed to rutile-type by anatase titanium dioxide, its principle may be SnO
2with rutile TiO
2there is similar microtexture, SnO
2act as the nucleus of Rutile Type.But, SnO
2mix, can change the color of nacreous mica pigment, add in the difficulty, particularly Sn controlling constant product quality normal containing heavy metal lead, the application (as makeup, toy for children etc.) for field of Environment Protection can be restricted.
In addition, current developed nacreous mica pigment is mostly single coat structure from structure, namely on mica substrate, only covers one deck water white transparency or coloured metal oxide film.Early, Technical comparing is ripe in single coating nacreous mica pigment exploitation, but single coating nacreous mica pigment due to its hide performance and tinctorial property poor, the application of some special occasions is subject to a definite limitation.
Summary of the invention
The object of the invention is to solve the deficiencies in the prior art, there is provided one not containing heavy metal ion (as: cadmium, lead, mercury, sexavalent chrome etc.), instead of tin ion promotor in traditional technology, to improve the content of synthetic mica surface rutile titanium dioxide coating layer, the surface luster of pearly pigment can be regulated simultaneously, there is the preparation method of the multifunctional magnetic synthetic mica pearlescent pigment of excellent weather resistance.
Object of the present invention is achieved by the following technical programs:
A preparation method for multifunctional magnetic synthetic mica pearlescent pigment, comprises the following steps:
The synthesis of S1, template: one or more halogenide hybrid reactions make template;
The preparation of S2, matrix: the ratio mixing by rare-earth oxide, sulphur powder, sodium carbonate, potassiumphosphate being 1.8 ~ 2:7.0 ~ 7.5:2.5 ~ 3:0.15 ~ 0.18 in molar ratio, after mixing, the template obtained with S1 mixes, namely form matrix, wherein the weight of template accounts for the 30%-50% of matrix total amount;
S3, the matrix obtained by S2 and synthetic mica are in molar ratio for the ratio of 0.5:100 ~ 1:100 is mixed to form mixture, mixture is dropped in Ball-stirring mill, add the grinding aid of 1 ‰ of synthetic mica, mill under 35% water content and 100r/min speed conditions 160 minutes, until the particle diameter of synthetic mica reach requirement and mixing of materials evenly after, just material is dried at about 150 DEG C and calcined 1 hour under the condition of 600 DEG C-900 DEG C, taking-up settling methods carries out classification and obtains rare-earth oxide sulfate high-visibility pigment afterwards;
S4, rare-earth oxide sulfate high-visibility pigment deionized water classification being reached Particle size requirements are made into the suspension that mass concentration is 10%, be warmed up to 65 DEG C-85 DEG C, add the titanium tetrachloride solution of 2M concentration, and keep pH value 2.0 ~ 2.1 with sodium hydroxide solution, stop adding titanium tetrachloride and sodium hydroxide solution when pigment form and aspect reach assign colors phase time, stir 30 minutes;
S5, suspension temperature is controlled between 75 DEG C ~ 85 DEG C, pH value remains between 6 ~ 9, add boric acid or the borax of 1% ~ 5%, the mixed solution adding calcium chloride or magnesium chloride or calcium chloride and the magnesium chloride accounting for suspension quality 1% ~ 5% again keeps the stable of suspension pH value, stir 30 minutes, reactant taken out filtration, washing, dry, calcine at 800 DEG C-860 DEG C, after cooling, gained is exactly weather-proof level synthetic mica pearly pigment, i.e. rutile TiO
2coated synthetic mica pearly pigment base-material, referred to as mica titanium; Wherein, with borate or phosphoric acid salt, coating is carried out to the outermost layer of weather resistant pearly pigment, pearly pigment use properties under severe conditions can be improved.
S6, Fe
3o
4coating: by the rutile TiO in S5
2coated synthetic mica pearly pigment base-material again drop in reactor, the ratio being 1:10 ~ 1:12 in solid-to-liquid ratio adds water and stirs, add ammonium chloride or the ammonium sulfate of 3%-5%, stirring is warming up to 80-85 DEG C, simultaneously add the iron protochloride of 1.0mol/L or copperas solution and 1.0mol/L potassium chlorate solution with the speed of 40ml/h, wherein, the ratio of iron protochloride or copperas solution and potassium chlorate solution is 1:1, and by alkali control ph 8.8 to 9.2, until solution adds, after reactant adds, continue to stir 0.5h, make reaction more complete, and the product suction filtration that S6 is finally obtained, washing, vacuum-drying at 60 DEG C, last under nitrogen atmosphere, calcine 3h at 350 DEG C, the pearly pigment of obtained black, be multifunctional magnetic synthetic mica pearlescent pigment, wherein in this step, add a certain amount of ammonium salt as buffer reagent, stability and the compactness of Z 250 can be improved, make Z 250 can form the nanometer thin layers of one deck even compact at mica surface, improve the magnetic behavior of particle,
S7, by the multifunctional magnetic synthetic mica pearlescent pigment Surface coating layer of metal cobalt that obtains in S6 or metallic nickel, thus effectively improve the metalluster of the stability of Z 250, magnetic coercive force and pigment, improve the magnetic behavior of particle.
Further, the general formula of described rare-earth oxide is Y
2o
3, wherein Y is one or both or the two or more composition in lanthanum, yttrium or gadolinium.
Further, in S3, synthetic mica sheet mill after fineness <200 μm.
Further, the halogenide in S1 is specially the muriate of basic metal, the fluorochemical of alkaline-earth metal and basic metal, alkaline-earth metal, and wherein basic metal is Li, Na, K, Rb or Cs, and alkaline-earth metal is Be, Mg, Ca, Sr or Ba.
Preferably, grinding aid can be selected: the sodium hexametaphosphate aqueous solution or tripolyphosphate sodium water solution or aqueous sodium carbonate or aqueous sodium hydroxide solution.
Preferably, in S6 iron ion covering amount at 12%-18%.
Further, the coated concrete steps of cobalt salt and nickel salt are: the multifunctional magnetic synthetic mica pearlescent pigment obtained in S6 again dropped in reactor, by solid-to-liquid ratio 1:10 to 1:12, add water and stir, rise to 85 DEG C, add soluble cobalt or the nickel salt of 5% of the dry powder amount of multifunctional magnetic synthetic mica pearlescent pigment, with reductive agent to cobalt salt, nickel salt reduces, the metal particle restored is made to be coated on pigment substrate surface, in the process of reduction plated film, need buffer reagent, as POTASSIUM BOROHYDRIDE controls size and the speed of response of the nano particle of metal Co or Ni, the nano-particle layer of smooth densification can be formed in surface of pigments, wherein, the mass ratio of buffer reagent and soluble cobalt or nickel salt is 1:1.
Preferably, described reductive agent is formaldehyde or POTASSIUM BOROHYDRIDE or glucose or inferior sodium phosphate.
The present invention has following advantage:
1, natural mica is substituted with synthetic mica, not containing heavy metal ion (as: cadmium, lead, mercury, sexavalent chrome etc.), as the base material of weathering and environment-friendly type pearly pigment;
2, on synthesis technique, utilize rare-earth oxide sulfate as promotor, instead of tin ion promotor in traditional technology, to improve the content of synthetic mica surface rutile titanium dioxide coating layer;
3, at TiO
2the nano-particle layer of layer outside coated ferriferrous oxide or cobalt metal or nickel, not only can regulate the surface luster of pearly pigment, and can give synthetic mica pearly pigment magnetic conduction function, is conducive to the shielding properties improving electromagnetic screen coating.
4, the intended application field of product that is suitable for of the present invention is extensive, be specially adapted to the paint with electromagnetic shielding function such as electronic apparatus, mobile phone, and the weather-proof level decorative paint used in the severe environment such as car paint, exterior coating, the advantage show excellent weather resistance, combining decoration functions with electro-magnetic screen function.
Embodiment
Below by embodiment, the present invention is described in further detail, but it is clearly understood that embodiments of the present invention are not limited thereto.
Embodiment 1
The synthesis of S1, template: by MgCl
2, Li
2cO
3, (NH
4)
2hPO
4, H
3bO
31:1:2:0.1 hybrid reaction and make template in molar ratio;
The preparation of S2, matrix: the ratio mixing by lanthanum trioxide, sulphur powder, sodium carbonate, potassiumphosphate being 1.9:7.3:2.7:0.16 in molar ratio, after mixing, the template obtained with S1 mixes, and namely form matrix, wherein the weight of template accounts for 30% of matrix total amount;
S3, the matrix obtained by S2 and synthetic mica are in molar ratio for the ratio of 0.5:100 is mixed to form mixture, mixture is dropped in Ball-stirring mill, add the sodium hexametaphosphate aqueous solution of 1 ‰ of synthetic mica, mill under 35% water content and 100r/min speed conditions 160 minutes, until the particle diameter fineness <200 of synthetic mica μm and mixing of materials evenly after, just material is dried at about 150 DEG C and calcined 1 hour under the condition of 700 DEG C, taking-up settling methods carries out classification and obtains rare-earth oxide sulfate high-visibility pigment afterwards;
S4, rare-earth oxide sulfate high-visibility pigment deionized water classification being reached Particle size requirements are made into the suspension that mass concentration is 10%, be warmed up to 75 DEG C, add the titanium tetrachloride solution of 2M concentration, and keep pH value 2.0 ~ 2.1 with sodium hydroxide solution, stop adding titanium tetrachloride and sodium hydroxide solution when pigment form and aspect reach assign colors phase time, stir 30 minutes;
S5, suspension temperature is controlled between 80 DEG C, pH value remains between 6 ~ 9, add the boric acid of 2%, the mixed solution adding calcium chloride or magnesium chloride or calcium chloride and the magnesium chloride accounting for suspension quality 2% again keeps the stable of suspension pH value, stir 30 minutes, reactant taken out filtration, washing, dry, calcine at 800 DEG C, after cooling, gained is exactly weather-proof level synthetic mica pearly pigment, i.e. rutile TiO
2coated synthetic mica pearly pigment base-material, referred to as mica titanium;
S6, by the rutile TiO in S5
2coated synthetic mica pearly pigment base-material again drop in reactor, the ratio being 1:10 in solid-to-liquid ratio adds water and stirs, add the ammonium chloride of 4%, stirring is warming up to 80-85 DEG C, add iron protochloride and the 1.0mol/L potassium chlorate solution of 1.0mol/L with the speed of 40ml/h simultaneously, wherein, the ratio of solution of ferrous chloride and potassium chlorate solution is 1:1, also stream adds the solution of ferrous chloride and potassium chlorate solution that prepare in advance simultaneously, and by alkali control ph 8.8 to 9.2, until solution adds, after reactant adds, continue to stir 0.5h, make reaction more complete, make Z 250 can form the nanometer thin layers of one deck even compact at mica surface, and the product suction filtration that S6 is finally obtained, washing, vacuum-drying at 60 DEG C, last under nitrogen atmosphere, calcine 3h, the pearly pigment of obtained black at 350 DEG C, wherein in this step, iron ion covering amount is 15%,
Embodiment 2
The synthesis of S1, template: by LiCl, CaCl
2template is mixed and made into 1:2;
The preparation of S2, matrix: the ratio mixing by yttrium oxide, sulphur powder, sodium carbonate, potassiumphosphate being 1.8:7.0:2.5:0.15 in molar ratio, after mixing, the template obtained with S1 mixes, and namely form matrix, wherein the weight of template accounts for 40% of matrix total amount;
S3, the matrix obtained by S2 and synthetic mica are in molar ratio for the ratio of 1:100 is mixed to form mixture, mixture is dropped in Ball-stirring mill, add the tripolyphosphate sodium water solution of 1 ‰ of synthetic mica, mill under 35% water content and 100r/min speed conditions 160 minutes, until the fineness <200 of synthetic mica μm and mixing of materials evenly after, just material is dried at about 150 DEG C and calcined 1 hour under the condition of 600 DEG C, taking-up settling methods carries out classification and obtains rare-earth oxide sulfate high-visibility pigment afterwards;
S4, rare-earth oxide sulfate high-visibility pigment deionized water classification being reached Particle size requirements are made into the suspension that mass concentration is 10%, be warmed up to 65 DEG C, add the titanium tetrachloride solution of 2M concentration, and keep pH value 2.0 ~ 2.1 with sodium hydroxide solution, stop adding titanium tetrachloride and sodium hydroxide solution when pigment form and aspect reach assign colors phase time, stir 30 minutes;
S5, suspension temperature is controlled between 75 DEG C ~ 85 DEG C, pH value remains between 6 ~ 9, add the borax of 1%, add the magnesium chloride accounting for suspension quality 1% again and keep the stable of suspension pH value, stir 30 minutes, reactant taken out filtration, washing, dry, calcine at 800 DEG C, after cooling, gained is exactly weather-proof level synthetic mica pearly pigment, i.e. rutile TiO
2coated synthetic mica pearly pigment base-material.
S6, Fe
3o
4coating: by the rutile TiO in S5
2coated synthetic mica pearly pigment base-material again drop in reactor, the ratio being 1:10 in solid-to-liquid ratio adds water and stirs, and adds the ammonium sulfate of 3%, stirs and is warming up to 80 DEG C, add solution of ferrous chloride and the 1.0mol/L potassium chlorate solution of 1.0mol/L with the speed of 40ml/h simultaneously, wherein, the ratio of solution of ferrous chloride and potassium chlorate solution is 1:1, and by alkali control ph 8.8 to 9.2, until solution adds, after reactant adds, continue to stir 0.5h, make reaction more complete; And the product suction filtration that S6 is finally obtained, washing, vacuum-drying at 60 DEG C; Last under nitrogen atmosphere, calcine 3h at 350 DEG C, the pearly pigment of obtained black, be multifunctional magnetic synthetic mica pearlescent pigment, wherein in this step, iron ion covering amount is 12%.
Embodiment 3
The synthesis of S1, template: by NaCl, MgCl
2, BaCl
2template is mixed and made into 1:1:2;
The preparation of S2, matrix: the ratio mixing by gadolinium sesquioxide, sulphur powder, sodium carbonate, potassiumphosphate being 2:7.5:3:0.18 in molar ratio, after mixing, the template obtained with S1 mixes, and namely form matrix, wherein the weight of template accounts for 50% of matrix total amount;
S3, the matrix obtained by S2 and synthetic mica are in molar ratio for the ratio of 1:100 is mixed to form mixture, mixture is dropped in Ball-stirring mill, add the aqueous sodium carbonate of 1 ‰ of synthetic mica, mill under 35% water content and 100r/min speed conditions 160 minutes, until the particle diameter fineness <200 μm of synthetic mica, and after mixing, just material is dried at about 150 DEG C and calcined 1 hour under the condition of 900 DEG C, taking-up settling methods carries out classification and obtains rare-earth oxide sulfate high-visibility pigment afterwards;
S4, rare-earth oxide sulfate high-visibility pigment deionized water classification being reached Particle size requirements are made into the suspension that mass concentration is 10%, be warmed up to 85 DEG C, add the titanium tetrachloride solution of 2M concentration, and keep pH value 2.0 ~ 2.1 with sodium hydroxide solution, stop adding titanium tetrachloride and sodium hydroxide solution when pigment form and aspect reach assign colors phase time, stir 30 minutes;
S5, suspension temperature is controlled between 75 DEG C ~ 85 DEG C, pH value remains between 6 ~ 9, add boric acid or the borax of 1% ~ 5%, add again and account for the calcium chloride of suspension quality 5% and the mixed solution of magnesium chloride, keep the stable of suspension pH value, stir 30 minutes, reactant taken out filtration, washing, dry, calcine at 860 DEG C, after cooling, gained is exactly weather-proof level synthetic mica pearly pigment, i.e. rutile TiO
2coated synthetic mica pearly pigment base-material, referred to as mica titanium;
S6, Fe
3o
4coating: by the rutile TiO in S5
2coated synthetic mica pearly pigment base-material again drop in reactor, the ratio being 1:12 in solid-to-liquid ratio adds water and stirs, and adds the ammonium chloride of 5%, stirs and is warming up to 80-85 DEG C, add copperas solution and the 1.0mol/L potassium chlorate solution of 1.0mol/L with the speed of 40ml/h simultaneously, wherein, the ratio of copperas solution and potassium chlorate solution is 1:1, and by alkali control ph 8.8 to 9.2, until solution adds, after reactant adds, continue to stir 0.5h, make reaction more complete; And the product suction filtration that S6 is finally obtained, washing, vacuum-drying at 60 DEG C; Last under nitrogen atmosphere, calcine 3h at 350 DEG C, the pearly pigment of obtained black, be multifunctional magnetic synthetic mica pearlescent pigment, wherein in this step, iron ion covering amount is 18%.
S7, cobalt salt and nickel salt coated: the multifunctional magnetic synthetic mica pearlescent pigment obtained in S6 is dropped in reactor again, by solid-to-liquid ratio 1:12, add water and stir, be warming up to 85 DEG C, add soluble cobalt or the nickel salt of 5% of the dry powder amount of multifunctional magnetic synthetic mica pearlescent pigment, by POTASSIUM BOROHYDRIDE to cobalt salt, nickel salt reduces, the metal particle restored is made to be coated on pigment substrate surface, simultaneously, in the process of reduction plated film, add POTASSIUM BOROHYDRIDE as buffer reagent to control size and the speed of response of the nano particle of metal Co or Ni, the nano-particle layer of smooth densification can be formed in surface of pigments, wherein, the mass ratio of buffer reagent and soluble cobalt or nickel salt is 1:1.
Embodiment 4
The synthesis of S1, template: by KCl, RbCl, BeCl
2, SrCl
2template is mixed and made into 1:1:2:1;
The preparation of S2, matrix: the ratio mixing by the mixture of lanthanum trioxide and yttrium oxide and gadolinium sesquioxide, sulphur powder, sodium carbonate, potassiumphosphate being 1.8:7.4:2.7:0.16 in molar ratio, after mixing, the template obtained with S1 mixes, namely form matrix, wherein the weight of template accounts for 35% of matrix total amount;
S3, the matrix obtained by S2 and synthetic mica are in molar ratio for the ratio of 0.7:100 is mixed to form mixture, mixture is dropped in Ball-stirring mill, add the sodium hexametaphosphate aqueous solution of 1 ‰ of synthetic mica, mill under 35% water content and 100r/min speed conditions 160 minutes, until the particle diameter of synthetic mica reach requirement and mixing of materials evenly after, just material is dried at about 150 DEG C and calcined 1 hour under the condition of 600 DEG C-900 DEG C, taking-up settling methods carries out classification and obtains rare-earth oxide sulfate high-visibility pigment afterwards;
S4, rare-earth oxide sulfate high-visibility pigment deionized water classification being reached Particle size requirements are made into the suspension that mass concentration is 10%, be warmed up to 65 DEG C-85 DEG C, add the titanium tetrachloride solution of 2M concentration, and keep pH value 2.0 ~ 2.1 with sodium hydroxide solution, stop adding titanium tetrachloride and sodium hydroxide solution when pigment form and aspect reach assign colors phase time, stir 30 minutes;
S5, suspension temperature is controlled between 75 DEG C ~ 85 DEG C, pH value remains between 6 ~ 9, add boric acid or the borax of 1% ~ 5%, the mixed solution adding calcium chloride or magnesium chloride or calcium chloride and the magnesium chloride accounting for suspension quality 1% ~ 5% again keeps the stable of suspension pH value, stir 30 minutes, reactant taken out filtration, washing, dry, calcine at 850 DEG C, after cooling, gained is exactly weather-proof level synthetic mica pearly pigment, i.e. rutile TiO
2coated synthetic mica pearly pigment base-material, referred to as mica titanium;
S6, Fe
3o
4coating: by the rutile TiO in S5
2coated synthetic mica pearly pigment base-material again drop in reactor, the ratio being 1:11 in solid-to-liquid ratio adds water and stirs, add person's ammonium sulfate of 3%, stirring is warming up to 80-85 DEG C, add copperas solution and the 1.0mol/L potassium chlorate solution of 1.0mol/L with the speed of 40ml/h simultaneously, wherein, the ratio of copperas solution and potassium chlorate solution is 1:1, and by alkali control ph 8.8 to 9.2, until solution adds, after reactant adds, continue to stir 0.5h, make reaction more complete; And the product suction filtration that S6 is finally obtained, washing, vacuum-drying at 60 DEG C; Last under nitrogen atmosphere, calcine 3h at 350 DEG C, the pearly pigment of obtained black, be multifunctional magnetic synthetic mica pearlescent pigment, in this step, iron ion covering amount is 14%.
Embodiment 5
S1 ~ the S6 of this embodiment is consistent with embodiment 1, and difference is, embodiment adds S7:
S7, cobalt salt and nickel salt coated: the multifunctional magnetic synthetic mica pearlescent pigment obtained in S6 is dropped in reactor again, by solid-to-liquid ratio 1:11, add water and stir, be warming up to 85 DEG C, add soluble cobalt or the nickel salt of 5% of the dry powder amount of multifunctional magnetic synthetic mica pearlescent pigment, by glucose or inferior sodium phosphate to cobalt salt, nickel salt reduces, the metal particle restored is made to be coated on pigment substrate surface, simultaneously, in the process of reduction plated film, add POTASSIUM BOROHYDRIDE as buffer reagent to control size and the speed of response of the nano particle of metal Co or Ni, the nano-particle layer of smooth densification can be formed in surface of pigments, wherein, the mass ratio of buffer reagent and soluble cobalt or nickel salt is 1:1.
Embodiment 6
S1 ~ the S6 of this embodiment is consistent with embodiment 2, and difference is, embodiment adds S7:
S7, cobalt salt and nickel salt coated: the multifunctional magnetic synthetic mica pearlescent pigment obtained in S6 is dropped in reactor again, by solid-to-liquid ratio 1:10, add water and stir, be warming up to 85 DEG C, add soluble cobalt or the nickel salt of 5% of the dry powder amount of multifunctional magnetic synthetic mica pearlescent pigment, with formaldehyde to cobalt salt, nickel salt reduces, the metal particle restored is made to be coated on pigment substrate surface, simultaneously, in the process of reduction plated film, add POTASSIUM BOROHYDRIDE as buffer reagent to control size and the speed of response of the nano particle of metal Co or Ni, the nano-particle layer of smooth densification can be formed in surface of pigments, wherein, the mass ratio of buffer reagent and soluble cobalt or nickel salt is 1:1.
To embodiment 1 ~ embodiment 6, the technical indicator of the coated synthetic mica pearly pigment base-material of rutile TiO_2 is as follows:
Outward appearance: there is nacreous powder; Brightness: be similar to ~ be better than; Color: approximate ~ micro-; Size-grade distribution: basically identical; Foreign matter content (%)≤0.10; 105 DEG C of volatile matters (%)≤0.50; Oil number (g/100g): 60 ~ 90; Aqeous suspension specific conductivity (us/cm)≤200; Aqeous suspension pH value: 6.0 ~ 10.0; Loose density (g/ml): 0.15 ~ 0.30; Heavy metal content (mg/kg): Cr+6<2, Pb<2, Hg<1, Cd<2; Temperature tolerance (DEG C) >=1250; Artificial weathering is tested: make product digestion time 2500 hours without variable color, and within 3500 hours, occur 1 grade of (very slight) variable color, efflorescence, crackle, foaming and obscission appear in nothing.
In addition, table 1 is some Performance comparision of product prepared by embodiments of the invention and traditional technology:
Some Performance comparision of the product that table 1 is prepared for embodiments of the invention and traditional technology
It can thus be appreciated that product prepared by the present invention has incomparable advantage.
Claims (8)
1. a preparation method for multifunctional magnetic synthetic mica pearlescent pigment, is characterized in that, comprises the following steps:
The synthesis of S1, template: one or more halogenide hybrid reactions make template; By MgCl
2, Li
2cO
3, (NH
4)
2hPO
4, H
3bO
31:1:2:0.1 hybrid reaction and make template in molar ratio;
The preparation of S2, matrix: the ratio mixing by rare-earth oxide, sulphur powder, sodium carbonate, potassiumphosphate being 1.8 ~ 2:7.0 ~ 7.5:2.5 ~ 3:0.15 ~ 0.18 in molar ratio, after mixing, the template obtained with S1 mixes, namely form matrix, wherein the weight of template accounts for the 30%-50% of matrix total amount;
S3, the matrix obtained by S2 and synthetic mica are in molar ratio for the ratio of 0.5:100 ~ 1:100 is mixed to form mixture, mixture is dropped in Ball-stirring mill, add the grinding aid of 1 ‰ of synthetic mica, mill under 35% water content and 100r/min speed conditions 160 minutes, until the particle diameter of synthetic mica reach requirement and mixing of materials evenly after, just material is dried at about 150 DEG C and calcined 1 hour under the condition of 600 DEG C-900 DEG C, taking-up settling methods carries out classification and obtains rare-earth oxide sulfate high-visibility pigment afterwards;
S4, rare-earth oxide sulfate high-visibility pigment deionized water classification being reached Particle size requirements are made into the suspension that mass concentration is 10%, be warmed up to 65 DEG C-85 DEG C, add the titanium tetrachloride solution of 2M concentration, and keep pH value 2.0 ~ 2.1 with sodium hydroxide solution, stop adding titanium tetrachloride and sodium hydroxide solution when pigment form and aspect reach assign colors phase time, stir 30 minutes;
S5, suspension temperature is controlled between 75 DEG C ~ 85 DEG C, pH value remains between 6 ~ 9, add boric acid or the borax of 1% ~ 5%, the mixed solution adding calcium chloride or magnesium chloride or calcium chloride and the magnesium chloride accounting for suspension quality 1% ~ 5% again keeps the stable of suspension pH value, stir 30 minutes, reactant taken out filtration, washing, dry, calcine at 800 DEG C-860 DEG C, after cooling, gained is exactly weather-proof level synthetic mica pearly pigment, i.e. rutile TiO
2coated synthetic mica pearly pigment base-material;
S6, Fe
3o
4coating: by the rutile TiO in S5
2coated synthetic mica pearly pigment base-material again drop in reactor, the ratio being 1:10 ~ 1:12 in solid-to-liquid ratio adds water and stirs, add ammonium chloride or the ammonium sulfate of 3%-5%, stirring is warming up to 80-85 DEG C, simultaneously add the iron protochloride of 1.0mol/L or copperas solution and 1.0mol/L potassium chlorate solution with the speed of 40ml/h, wherein, the ratio of iron protochloride or copperas solution and potassium chlorate solution is 1:1, and by alkali control ph 8.8 to 9.2, until solution adds, after reactant adds, continue to stir 0.5h, make reaction more complete, and the product suction filtration that S6 is finally obtained, washing, vacuum-drying at 60 DEG C, last under nitrogen atmosphere, calcine 3h at 350 DEG C, the pearly pigment of obtained black, is multifunctional magnetic synthetic mica pearlescent pigment,
S7, by the multifunctional magnetic synthetic mica pearlescent pigment Surface coating layer of metal cobalt that obtains in S6 or metallic nickel.
2. the preparation method of multifunctional magnetic synthetic mica pearlescent pigment according to claim 1, is characterized in that, the general formula of described rare-earth oxide is Y
2o
3, wherein Y is one or both or the two or more composition in lanthanum, yttrium or gadolinium.
3. the preparation method of multifunctional magnetic synthetic mica pearlescent pigment according to claim 1, it is characterized in that, halogenide in S1 is specially the muriate of basic metal, the fluorochemical of alkaline-earth metal and basic metal, alkaline-earth metal, wherein basic metal is Li, Na, K, Rb or Cs, and alkaline-earth metal is Be, Mg, Ca, Sr or Ba.
4. the preparation method of multifunctional magnetic synthetic mica pearlescent pigment according to claim 1, is characterized in that, in S3, synthetic mica sheet mill after fineness <200 μm.
5. the preparation method of multifunctional magnetic synthetic mica pearlescent pigment according to claim 1, is characterized in that, grinding aid can be selected: the sodium hexametaphosphate aqueous solution or tripolyphosphate sodium water solution or aqueous sodium carbonate or aqueous sodium hydroxide solution.
6. the preparation method of multifunctional magnetic synthetic mica pearlescent pigment according to claim 1, is characterized in that, in S6, iron ion covering amount is at 12%-18%.
7. the preparation method of multifunctional magnetic synthetic mica pearlescent pigment according to claim 1, it is characterized in that, the coated concrete steps of cobalt salt and nickel salt are: the multifunctional magnetic synthetic mica pearlescent pigment obtained in S6 again dropped in reactor, by solid-to-liquid ratio 1:10 to 1:12, add water and stir, rise to 85 DEG C, add soluble cobalt or the nickel salt of 5% of the dry powder amount of multifunctional magnetic synthetic mica pearlescent pigment, with reductive agent to cobalt salt, nickel salt reduces, the metal particle restored is made to be coated on pigment substrate surface, in the process of reduction plated film, add POTASSIUM BOROHYDRIDE as buffer reagent to control size and the speed of response of the nano particle of metal Co or Ni, the nano-particle layer of smooth densification can be formed in surface of pigments, wherein, the mass ratio of buffer reagent and soluble cobalt or nickel salt is 1:1.
8. the preparation method of multifunctional magnetic synthetic mica pearlescent pigment according to claim 7, is characterized in that, described reductive agent is formaldehyde or POTASSIUM BOROHYDRIDE or glucose or inferior sodium phosphate.
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| CN113773670A (en) * | 2020-06-09 | 2021-12-10 | 惠州市华阳光学技术有限公司 | Photochromic pigment and preparation method thereof |
| CN112662201B (en) * | 2020-12-21 | 2021-10-22 | 江西善纳新材料科技有限公司 | Preparation method of mica-based fluorescent pearlescent pigment |
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