CN103224717B - Preparation method of composite coating titanium dioxide pigment - Google Patents
Preparation method of composite coating titanium dioxide pigment Download PDFInfo
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- CN103224717B CN103224717B CN201310086971.8A CN201310086971A CN103224717B CN 103224717 B CN103224717 B CN 103224717B CN 201310086971 A CN201310086971 A CN 201310086971A CN 103224717 B CN103224717 B CN 103224717B
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Abstract
The invention discloses a preparation method of a composite coating titanium dioxide pigment. The preparation method comprises the following steps: simultaneously adding a common precipitating agent comprising a phosphoric water-soluble compound and an inorganic acid or inorganic base, and a water-soluble salt containing aluminum, zirconium, cerium, zinc, magnesium or tin to initial dispersed titanium dioxide, and coating the surface of the initial titanium dioxide with a layer of a mixed coat including a phosphate compound and an insoluble hydroxide. The pigment prepared through the method has the advantages of high light resistance, excellent covering power, and excellent oily whiteness, and can be used in coatings, plastics and papermaking.
Description
Technical field
The present invention relates to field prepared by TiO 2 pigment, particularly relate to a kind of preparation method of TiO 2 pigment of composite coated raising light permanency.
Background technology
Specific refractory power is high because having for titanium dioxide, reducing power is strong, glossiness and the advantage such as whiteness is good and become best white pigment, is widely used in the fields such as coating, plastics, papermaking, ink and chemical fibre.But due to titanium dioxide particularly rutile titanium dioxide there is photocatalytic activity, in use can the organic composition that contacts with it of catalyzed degradation, make the matrix contacted with it produce the phenomenon such as loss of gloss and powder of detached.When being used in decorative paper, when decorative laminate is exposed to the sun under being placed on daylight or ultraviolet, will photochemical reaction be there is in titanium dioxide, generate unstable titanous (gloomy), because titanium dioxide is in the environment of isolating oxygen, titanous can not react with the oxygen in air and be recovered to titanic in time.When the prolongation titanous along with the time of being exposed to the sun will be cumulative, therefore decorative laminate tarnishes and just there will be aging phenomenon.Due to the photocatalytic activity of titanium dioxide, the serious performance and used life reducing various product.
In order to suppress the photocatalytic activity of titanium dioxide, usually carry out special process to reach the light permanency that can apply on the surface of titanium dioxide.Known to one or more layers silicon oxide of titanium dioxide granule surface-coated in this area, aluminum oxide, difficultly-soluble phosphates compound, sometimes also can in coat the oxide compound of the metal such as doped tin, cerium, vanadium.Those skilled in the art study discovery recently, more can improve the light permanency of TiO 2 pigment at titanium dioxide surface coated phosphate than independent cladded aluminium hydroxide, zirconium hydroxide etc.In the process of precipitate phosphoric acid salt, the while of meeting, the oxyhydroxide of the indissoluble that molten phosphatic metal ion in distress is corresponding generates.
Summary of the invention
The invention provides a kind of preparation method of composite coated TiO 2 pigment, the pigment adopting this preparation method to obtain has very high light permanency.
A preparation method for composite coated TiO 2 pigment, comprises following step:
(1) titanium dioxide first product is scattered in the aqeous suspension A obtaining titanium dioxide first product in distilled water or deionized water;
(2) react joining containing the water-soluble salt of the first metal and the first precipitation agent in aqeous suspension A that step (1) obtains simultaneously, obtain aqeous suspension B;
The first described metal is aluminium, zirconium, cerium, zinc, magnesium or tin;
The first described metal is present in its water-soluble salt with the form of acid ion or metallic cation;
The first described precipitation agent is made up of components I and compositionⅱ;
Described components I is the water-soluble cpds of phosphorus;
Described compositionⅱ is mineral acid or mineral alkali;
(3) react joining containing bimetallic water-soluble salt and the second precipitation agent in aqeous suspension B that step (2) obtains simultaneously, obtain aqeous suspension C;
The second described metal is aluminium, zirconium, silicon, zinc or magnesium;
The second described metal is present in its water-soluble salt with the form of acid ion or metallic cation;
The second described precipitation agent is mineral acid or mineral alkali;
(4) pH value to 5 ~ 8 of aqeous suspension C that obtain of regulating step (3), then after filtration, washing, dry and comminution by gas stream, obtain described composite coated TiO 2 pigment.
In step of the present invention (2), the phosphoric acid salt generating insoluble is reacted containing the water-soluble salt of the first metal and components I, the oxyhydroxide generating insoluble is reacted with compositionⅱ, phosphoric acid salt and oxyhydroxide generate simultaneously, one deck mixing coat is obtained at the surface precipitation of titanium dioxide first product, in this mixing coat, phosphorus and atoms metal have certain ratio, and the mixing coat obtained is finer and close, thus make this pigment have higher light permanency.
In the present invention, by changing the order of operation steps, the mixing coat obtained can at the innermost layer of the whole coat of titanium dioxide, middle layer or outermost layer.
As preferably, in step (1), the preparation method of described aqeous suspension A is as follows:
A titanium dioxide first product is made into slurry with distilled water or deionized water by ();
B () adds dispersion agent and pH value is adjusted to 7 ~ 11 in the slurry in step (a), then in sand mill, use screen filtration after sand milling, obtain described aqeous suspension A.
In step (a), described titanium dioxide first product can be the rutile titanium dioxide produced by chlorination process, also can be the rutile-type by Production By Sulfuric Acid Process or anatase titanium dioxide, all can select commercially available prod.As further preferred, described titanium dioxide first product selects the titanium dioxide substantially with rutile-type structure.To the not special requirement of the concentration of titanium dioxide first product in slurry, preferably, the concentration containing titanium dioxide first product in slurry is 100g/L ~ 500g/L.
In step (b), described dispersion agent is one or both in water glass, Sodium hexametaphosphate 99, and the mass ratio of described dispersion agent and titanium dioxide first product is 0.1 ~ 0.5:100.Water glass and Sodium hexametaphosphate 99 can adopt the mode of the aqueous solution to add, by adding above-mentioned dispersion agent, on the one hand due to volume effect, titanium dioxide first product is made to be evenly dispersed in slurry system, on the other hand, owing to there is steric effect, to make between solid particulate because of electrostatic repulsion away from, thus make solid particulate not easily agglomeration occur, dispersion system is even, particle suspension property increases, thus makes follow-up sanding step have better effect.
In step (b), regulate by adding the pH value of alkaline solution to slurry, this alkaline solution is aqueous sodium hydroxide solution, potassium hydroxide aqueous solution, ammonia soln or aqueous sodium carbonate.
In step (2), the water-soluble salt containing the first metal can be the water soluble salt of aluminium, zirconium, cerium, zinc, magnesium or tin etc., concrete as Tai-Ace S 150, sodium metaaluminate, zirconium sulfate, cerous nitrate, zinc chloride or magnesium chloride etc.The add-on of these water-soluble salts is 0.5% ~ 5% of titanium dioxide first product add-on, and the add-on of water-soluble salt is in the quality of its maxivalence metal oxide, and the add-on of titanium dioxide first product is with TiO
2quality meter.
In step (2), described components I is the water-soluble cpds of phosphorus, and specifically can select the one in alkali metal phosphate, ammonium phosphate, polyphosphate, phosphoric acid etc., when the first metal exists with the form of acid ion, components I is phosphoric acid; When the first metal exists with the form of metallic cation, components I is alkali metal phosphate, ammonium phosphate or polyphosphate.
The add-on of the water-soluble cpds of described phosphorus is 0.5% ~ 5.0% of titanium dioxide first product add-on, and the add-on of the water-soluble cpds of described phosphorus is with P
2o
5quality meter, titanium dioxide first product add-on is with TiO
2quality meter.
In step (2), in water-soluble salt, when the first metal exists with the form of acid ion, compositionⅱ is mineral acid; When the first metal exists with the form of metallic cation, compositionⅱ is mineral alkali, and both neutralization reaction occur and obtain precipitation of hydroxide, and the consumption of compositionⅱ calculates based on the basicity of the water-soluble salt that can neutralize or acidity.
As preferably, in step (2), the described water-soluble salt containing the first metal is sodium metaaluminate;
Described components I is phosphoric acid;
Described compositionⅱ is sulfuric acid.Now, the coat on the surface of the titanium dioxide first product in aqeous suspension B is insoluble aluminum phosphate and alumag, and the pigment light permanency finally obtained is high, and has excellent opacifying power, and the raw material used cheaply is easy to get.
As preferably, the mole dosage of described phosphoric acid and sulfuric acid is than being 1:0.1 ~ 5; As further preferred, the mole dosage of described phosphoric acid and sulfuric acid is than being 1:0.5 ~ 2, and now, in the coat obtained, the ratio of phosphorus and its atoms metal keeps certain scope, and coat has higher compactness.
As other preferred, in step (2), the described water-soluble salt containing the first metal is zirconium sulfate, cerous nitrate, magnesium chloride or zinc nitrate;
Described components I is Sodium phosphate dibasic or Sodium hexametaphosphate 99;
Described compositionⅱ is sodium hydroxide or potassium hydroxide.Now, coat on the surface of the titanium dioxide first product in aqeous suspension B is respectively insoluble zirconium phosphate and zirconium hydroxide mixture, Cerium monophosphate and cerous hydroxide mixture, trimagnesium phosphate and magnesium hydroxide mixture or zinc phosphate and zinc hydroxide mixture, the pigment light permanency finally obtained is high, and have excellent opacifying power, and the raw material used cheaply is easy to get.
As preferably, the mole dosage of described components I and compositionⅱ is than being 1:0.1 ~ 5; As further preferred, the mole dosage of described components I and compositionⅱ is than being 1:0.2 ~ 1.5, and in the coat now obtained, the ratio of phosphorus and its atoms metal keeps certain scope, and the compactness of coat is higher.
As preferably, in step (2), containing the first metal water-soluble salt and the first precipitation agent adopts and the mode flowed adds, and when flowing, keep pH constant.
As further preferably, in step (2), and keep pH to be 2 ~ 11 when flowing, be preferably 6 ~ 10, now can ensure the smooth generation of oxyhydroxide.
In step (2), the joining day of water-soluble salt is too short is easy to the throw out autohemagglutination making generation, instead of is formed uniformly the mixing coat of phosphoric acid salt and its oxyhydroxide, and the joining day long production efficiency that can reduce, add energy consumption simultaneously.So and the time of flowing be preferably 0.5h ~ 5h, under this optimum condition, to make on the surface of titanium dioxide coated phosphate and its oxyhydroxide mixing coat preferably.
In step (3), react containing bimetallic water-soluble salt and the second precipitation agent, reaction is continued on the mixing coat surface obtained in step (2), coated other compounds upper, be preferably aluminium hydroxide, the concrete operations of this step are well known to those skilled in the art.
Wherein, the first described metal and the second metal can be same metal or not same metal.
Can be Tai-Ace S 150 containing bimetallic water-soluble salt, sodium metaaluminate, zirconium sulfate, zinc chloride or magnesium chloride.
Second precipitation agent can be sulfuric acid or sodium hydroxide.
The post-treating method of step (4) is well known to those skilled in the art, and dry temperature is preferably 100 DEG C ~ 300 DEG C.
Compared with the existing technology, the mixing coat of one deck densification is included in the pigment that preparation method of the present invention obtains, wherein, the ratio of phosphorus and atoms metal can control, there is very high light permanency, and there is excellent opacifying power and oiliness whiteness, may be used in coating, plastics and papermaking.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope photo of the mixing coat of the coated complete aluminum phosphate of embodiment 1 titanium dioxide surface and aluminium hydroxide;
Fig. 2 is the transmission electron microscope photo of the titanium dioxide granule of the coated complete aluminum phosphate of comparative example 1A titanium dioxide surface and partial aluminum hydroxide (namely adding sodium aluminate solution in step 3);
Fig. 3 is the transmission electron microscope photo of the titanium dioxide granule after adding sodium aluminate solution in comparative example 1B step 3.
Embodiment
The performance test methods of the composite coated TiO 2 pigment that the present invention obtains is as follows: by TiO
2pigment evenly spreads in resin and applies film forming, irradiates certain hour under being placed in light source, can judge TiO
2light permanency.Concrete operating process is as follows, takes 1.20g TiO
2, join in 6.0mL melamine resin, get finely dispersed mixed solution 2.0mL and be evenly coated on slide glass, place it in 70 DEG C of oven dry in loft drier.Take out, put into Iodine gallium light printer and be exposed to the sun, containing three power in printer is the Iodine gallium light of 1000W, and sample is 50cm apart from the vertical range of Iodine gallium light.Be exposed to the sun after 2h and take out, test be exposed to the sun before and after aberration Δ E, Δ E is less, and light permanency is better.
Embodiment 1
1) with deionized water by 1000g titanium dioxide first product (by the anatase titanium dioxide of Production By Sulfuric Acid Process, Ningbo Xinfu Titanium Dioxide Co., Ltd.), the concentration be mixed with containing titanium dioxide first product is the slurry of 320g/L, add the sodium hexametaphosphate solution 0.05L that Sodium hexametaphosphate 99 mass concentration is 70g/L, add containing sodium hydroxide mass percent be 20% aqueous sodium hydroxide solution regulate pH to 8, then slurry is passed into sand milling in sand mill, slurry after sand milling, by screen cloth filtering coarse particles, obtains the aqeous suspension of titanium dioxide first product.
2) aqeous suspension of titanium dioxide first product is joined in coating tank, stir simultaneously and be warming up to 40 DEG C.
3) slowly add the sodium metaaluminate aqueous solution that concentration is 100g/L, add-on is that relative titanium dioxide first product add-on is (with TiO
2quality meter) 4.0%; Add massfraction be the phosphoric acid solution of 30% and flow maintenance pH=7 ~ 8, the add-on of phosphoric acid is that relative titanium dioxide first product add-on is (with TiO simultaneously
2quality meter) 3.0%, containing sulfuric acid in described phosphoric acid solution, the mol ratio of phosphoric acid and sulfuric acid is 1:0.5.
4) slowly add the aluminum sulfate aqueous solution that concentration is 100g/L, be 15% sulfuric acid with mass percent and stream joins in reaction paste, keep pH=8.The add-on of the sodium metaaluminate aqueous solution is (with Al
2o
3quality meter) for relative titanium dioxide first product add-on is (with TiO
2quality meter) 2.0%.
5) after the sodium metaaluminate aqueous solution adds, slaking 20min is stirred.Be 15% sulphur acid for adjusting pH to 7 with mass percent, stir slaking 40min, filter, with deionized water wash, dry, obtain final pigment combination product through comminution by gas stream.
For determining the effect according to the inventive method, and the coating degree of co-precipitation phosphate Aluminium hydroxide, we carry out light permanency test to the final pigment of preparation.
Comparative example 1A
Comparative example 1A phosphoric acid used does not mix sulfuric acid, respectively with phosphoric acid and sulfuric acid successively and sodium aluminate solution flowing.Other step is identical with embodiment 1.
Comparative example 1B does not use phosphoric acid, and directly sulfuric acid and sodium aluminate solution are flowed, other step is identical with embodiment 1.
The test result of pigment light permanency prepared by embodiment 1 and its comparative example is as table 1:
Table 1
| Light permanency (aberration) | Embodiment 1 | Embodiment 1A | Embodiment 1B |
| △E | 2.1 | 3.8 | 6.6 |
In upper table, the aberration of embodiment 1 is minimum, and sun-proof performance is best, shows that the aluminum phosphate of co-precipitation and aluminium hydroxide can improve the sun-proof performance of pigment.
Fig. 1 is the transmission electron microscope photo of the mixing coat of the coated complete aluminum phosphate of embodiment 1 titanium dioxide surface and aluminium hydroxide;
Fig. 2 is the transmission electron microscope photo of the titanium dioxide granule of the coated complete aluminum phosphate of comparative example 1A titanium dioxide surface and partial aluminum hydroxide (namely adding sodium aluminate solution in step 3).
Fig. 3 is the transmission electron microscope photo of the titanium dioxide granule after adding sodium aluminate solution in comparative example 1B step 3.
The coated dense uniform of mixing coat of aluminum phosphate and aluminium hydroxide in embodiment 1 can be found out from photo, and the particle that comparative example 1A does not adopt the titanium dioxide granule surface precipitation of mixing coating much not of uniform size, not coated uniformly, comparative example 1B has only precipitated aluminium hydroxide on titanium dioxide granule surface, be adsorbed on titanium dioxide granule surface as one deck tulle, there is no the coated of densification.Therefore adopt the coating method of patent of the present invention can prepare the coating layer of even compact, improve the light permanency of pigment finished product further.
Embodiment 2
With deionized water by 1000g titanium dioxide first product (by the rutile titanium dioxide of Production By Sulfuric Acid Process, Ningbo Xinfu Titanium Dioxide Co., Ltd.), being mixed with containing titanium dioxide first product concentration is the slurry of 280g/L, add the sodium silicate aqueous solution 0.03L that water glass mass concentration is 100g/L, add containing sodium hydroxide mass percent be 10% aqueous sodium hydroxide solution regulate pH to 9, then slurry is passed into sand milling in sand mill, slurry after sand milling, by screen cloth filtering coarse particles, obtains the aqeous suspension of titanium dioxide first product.
The aqeous suspension of titanium dioxide first product is joined in coating tank, stir simultaneously and be warming up to 60 DEG C.
Slowly add the zirconium sulfate aqueous solution that concentration is 100g/L, add-on is that relative titanium dioxide first product add-on is (with TiO
2quality meter) 4.0%; Add massfraction be the disodium phosphate soln of 30% and flow maintenance pH=2 ~ 2.5, the add-on of Sodium phosphate dibasic is that relative titanium dioxide first product add-on is (with TiO simultaneously
2quality meter) 3.0%, the sodium hydroxide contained in described disodium phosphate soln, the content of sodium hydroxide is based on can the acidity in neutralisation of sulphuric acid zirconium calculate.
Slowly add the aluminum sulfate aqueous solution that concentration is 150g/L, be 30% sodium hydroxide solution with mass percent and stream joins in reaction paste, keep pH=2 ~ 2.5.The add-on of aluminum sulfate aqueous solution is (with Al
2o
3quality meter) for relative titanium dioxide first product add-on is (with TiO
2quality meter) 3.0%.
After aluminum sulfate aqueous solution adds, stir slaking 15min.Be that 30% aqueous sodium hydroxide solution regulates pH to 7 with mass percent, stir slaking 30min, filter, with deionized water wash, dry, obtain final pigment combination product through comminution by gas stream.
For determining the effect according to the inventive method, and co-precipitation zirconium phosphate, the coating degree of zirconium hydroxide, we carry out light permanency test to the final pigment of preparation.
Comparative example 2A
Comparative example 2A Sodium phosphate dibasic used does not mix sodium hydroxide, respectively with Sodium phosphate dibasic and sodium hydroxide successively and zirconium sulfate solution flowing.Other step is identical with embodiment 2.
Comparative example 2B does not use Sodium phosphate dibasic, and directly sodium hydroxide and zirconium sulfate solution are flowed, other step is identical with embodiment 2.
The test result of pigment light permanency prepared by embodiment 2 and its comparative example is as following table:
Table 2
| Light permanency (aberration) | Embodiment 2 | Embodiment 2A | Embodiment 2B |
| △E | 3.1 | 4.1 | 5.5 |
In upper table, the aberration of embodiment 2 is minimum, and sun-proof performance is best, shows that the zirconium phosphate of co-precipitation and zirconium hydroxide can improve the sun-proof performance of pigment.
Embodiment 3
With deionized water by 1000g titanium dioxide first product (by the anatase titanium dioxide of Production By Sulfuric Acid Process, Ningbo Xinfu Titanium Dioxide Co., Ltd.), being mixed with containing titanium dioxide first product concentration is the slurry of 300g/L, add the sodium silicate aqueous solution 0.03L that water glass mass concentration is 100g/L, add containing sodium hydroxide mass percent be 10% aqueous sodium hydroxide solution regulate pH to 10, then slurry is passed into sand milling in sand mill, slurry after sand milling, by screen cloth filtering coarse particles, obtains the aqeous suspension of titanium dioxide first product.
The aqeous suspension of titanium dioxide first product is joined in coating tank, stir simultaneously and be warming up to 70 DEG C.
Slowly add the cerous nitrate aqueous solution that concentration is 100g/L, add-on is that relative titanium dioxide first product add-on is (with TiO
2quality meter) 0.8%; Add massfraction be the sodium hexametaphosphate solution of 25% and flow maintenance pH=10 ~ 10.5, the add-on of Sodium hexametaphosphate 99 is that relative titanium dioxide first product add-on is (with TiO simultaneously
2quality meter) 2.5%, containing sodium hydroxide in described sodium hexametaphosphate solution, the content of sodium hydroxide calculates based on the acidity in energy and in cerous nitrate.
Slowly add the aluminum sulfate aqueous solution that concentration is 150g/L, be 20% sulphuric acid soln with mass percent and stream joins in reaction paste, keep pH=10 ~ 10.5.The add-on of the sodium metaaluminate aqueous solution is (with Al
2o
3quality meter) for relative titanium dioxide first product add-on is (with TiO
2quality meter) 5.0%.
After the sodium metaaluminate aqueous solution adds, stir slaking 15min.Be that 20% sulphuric acid soln regulates pH to 7 with mass percent, stir slaking 30min, filter, with deionized water wash, dry, obtain final pigment combination product through comminution by gas stream.
For determining the effect according to the inventive method, and the coating degree of co-precipitation Cerium monophosphate and cerous hydroxide, we carry out light permanency test to the final pigment of preparation.
Comparative example 3A
Comparative example 3A Sodium hexametaphosphate 99 used does not mix sodium hydroxide, with respectively with Sodium hexametaphosphate 99 and sodium hydroxide successively and cerous nitrate solution flowing.Other step is identical with embodiment 3.
Comparative example 3B does not use Sodium hexametaphosphate 99, and directly sodium hydroxide and cerous nitrate solution are flowed, other step is identical with embodiment 3.
The test result of pigment light permanency prepared by embodiment 3 and its comparative example is as following table:
Table 3
| Light permanency (aberration) | Embodiment 3 | Embodiment 3A | Embodiment 3B |
| △E | 2.8 | 3.6 | 4.3 |
In upper table, the aberration of embodiment 3 is minimum, and sun-proof performance is best, shows that the Cerium monophosphate of co-precipitation and cerous hydroxide can improve the sun-proof performance of pigment.
Embodiment 4
With deionized water by 1000g titanium dioxide first product (rutile titanium dioxide produced by chlorination process), being mixed with containing titanium dioxide first product concentration is the slurry of 320g/L, add the sodium hexametaphosphate solution 0.05L that Sodium hexametaphosphate 99 mass concentration is 70g/L, add containing sodium hydroxide mass percent be 30% aqueous sodium hydroxide solution regulate pH to 8.5, then slurry is passed into sand milling in sand mill, slurry after sand milling, by screen cloth filtering coarse particles, obtains the aqeous suspension of titanium dioxide first product.
The aqeous suspension of titanium dioxide first product is joined in coating tank, stir simultaneously and be warming up to 60 DEG C.
Slowly add the magnesium chloride brine that concentration is 80g/L, add-on is that relative titanium dioxide first product add-on is (with TiO
2quality meter) 4%; Add massfraction be the disodium-hydrogen solution of 35% and flow maintenance pH=8 ~ 9, the add-on of disodium-hydrogen is that relative titanium dioxide first product add-on is (with TiO simultaneously
2quality meter) 3%, containing sodium hydroxide in described disodium-hydrogen solution, the content of sodium hydroxide calculates based on the acidity in energy and in magnesium chloride.
Slowly add the aluminum sulfate aqueous solution that concentration is 150g/L, be 20% sulphuric acid soln with mass percent and stream joins in reaction paste, keep pH=8 ~ 9.The add-on of the sodium metaaluminate aqueous solution is (with Al
2o
3quality meter) for relative titanium dioxide first product add-on is (with TiO
2quality meter) 2.5%.
After the sodium metaaluminate aqueous solution adds, stir slaking 15min.Be that 20% sulphuric acid soln regulates pH to 7 with mass percent, stir slaking 30min, filter, with deionized water wash, dry, obtain final pigment combination product through comminution by gas stream.
For determining the effect according to the inventive method, and the trimagnesium phosphate that forms sediment altogether, the coating degree of magnesium hydroxide, we carry out light permanency test to the final pigment of preparation.
Comparative example 4A
Comparative example 4A disodium-hydrogen used does not mix sodium hydroxide, with respectively with disodium-hydrogen and sodium hydroxide successively and magnesium chloride solution flowing.Other step is identical with embodiment 4.
Comparative example 4B does not use disodium-hydrogen, and directly sodium hydroxide and magnesium chloride solution are flowed, other step is identical with embodiment 4.
The test result of pigment light permanency prepared by embodiment 4 and its comparative example is as following table:
Table 4
| Light permanency (aberration) | Embodiment 4 | Embodiment 4A | Embodiment 4B |
| △E | 3.0 | 3.9 | 4.7 |
In upper table, the aberration of embodiment 4 is minimum, and sun-proof performance is best, shows that the trimagnesium phosphate of co-precipitation and magnesium hydroxide can improve the sun-proof performance of pigment.
Embodiment 5
With deionized water by 1000g titanium dioxide first product (rutile titanium dioxide produced by chlorination process), being mixed with containing titanium dioxide first product concentration is the slurry of 320g/L, add the sodium hexametaphosphate solution 0.05L that Sodium hexametaphosphate 99 mass concentration is 70g/L, add containing sodium hydroxide mass percent be 30% aqueous sodium hydroxide solution regulate pH to 8.5, then slurry is passed into sand milling in sand mill, slurry after sand milling, by screen cloth filtering coarse particles, obtains the aqeous suspension of titanium dioxide first product.
The aqeous suspension of titanium dioxide first product is joined in coating tank, stir simultaneously and be warming up to 80 DEG C.
Slowly add the zinc nitrate aqueous solution that concentration is 100g/L, add-on is that relative titanium dioxide first product add-on is (with TiO
2quality meter) 3%; Add massfraction be the sodium hexametaphosphate solution of 20% and flow maintenance pH=9 ~ 10, the add-on of Sodium hexametaphosphate 99 is that relative titanium dioxide first product add-on is (with TiO simultaneously
2quality meter) 3%, containing sodium hydroxide in described sodium hexametaphosphate solution, the content of sodium hydroxide calculates based on the acidity in energy and in zinc nitrate.
Slowly add the aluminum sulfate aqueous solution that concentration is 110g/L, be 15% sulphuric acid soln with mass percent and stream joins in reaction paste, keep pH=9 ~ 10.The add-on of the sodium metaaluminate aqueous solution is (with Al
2o
3quality meter) for relative titanium dioxide first product add-on is (with TiO
2quality meter) 3%.
After the sodium metaaluminate aqueous solution adds, stir slaking 20min.Be that 20% sulphuric acid soln regulates pH to 7 with mass percent, stir slaking 30min, filter, with deionized water wash, dry, obtain final pigment combination product through comminution by gas stream.
For determining the effect according to the inventive method, and the zinc phosphate that forms sediment altogether, the coating degree of zinc hydroxide, we carry out light permanency test to the final pigment of preparation.
Comparative example 5A
Comparative example 5A Sodium hexametaphosphate 99 used does not mix sodium hydroxide, with respectively with Sodium hexametaphosphate 99 and sodium hydroxide successively and zinc nitrate solution flowing.Other step is identical with embodiment 5.
Comparative example 5B does not use Sodium hexametaphosphate 99, and directly sodium hydroxide and zinc nitrate solution are flowed, other step is identical with embodiment 5.
The test result of pigment light permanency prepared by embodiment 5 and its comparative example is as following table:
Table 5
| Light permanency (aberration) | Embodiment 5 | Embodiment 5A | Embodiment 5B |
| △E | 2.4 | 3.7 | 5.0 |
In upper table, the aberration of embodiment 5 is minimum, and sun-proof performance is best, shows that the zinc phosphate of co-precipitation and zinc hydroxide can improve the sun-proof performance of pigment.
Claims (7)
1. a preparation method for composite coated TiO 2 pigment, is characterized in that, comprises following step:
(1) titanium dioxide first product is scattered in the aqeous suspension A obtaining titanium dioxide first product in distilled water or deionized water;
(2) react joining containing the water-soluble salt of the first metal and the first precipitation agent in aqeous suspension A that step (1) obtains simultaneously, obtain aqeous suspension B;
The first described metal is aluminium, zirconium, cerium, zinc, magnesium or tin;
The first described metal is present in its water-soluble salt with the form of acid ion or metallic cation;
The first described precipitation agent is made up of components I and compositionⅱ;
Described components I is the water-soluble cpds of phosphorus;
Described compositionⅱ is mineral acid or mineral alkali;
Containing the first metal water-soluble salt and the first precipitation agent adopts and the mode flowed adds;
(3) react joining containing bimetallic water-soluble salt and the second precipitation agent in aqeous suspension B that step (2) obtains simultaneously, obtain aqeous suspension C;
The second described metal is aluminium, zirconium, silicon, zinc or magnesium;
The second described metal is present in its water-soluble salt with the form of acid ion or metallic cation;
The second described precipitation agent is mineral acid or mineral alkali;
(4) pH value to 5 ~ 8 of aqeous suspension C that obtain of regulating step (3), then after filtration, washing, dry and comminution by gas stream, obtain described composite coated TiO 2 pigment.
2. the preparation method of composite coated TiO 2 pigment according to claim 1, is characterized in that, in step (2), the described water-soluble salt containing the first metal is sodium metaaluminate;
Described components I is phosphoric acid;
Described compositionⅱ is sulfuric acid.
3. the preparation method of composite coated TiO 2 pigment according to claim 2, is characterized in that, the mole dosage of described phosphoric acid and sulfuric acid is than being 1:0.1 ~ 5.
4. the preparation method of composite coated TiO 2 pigment according to claim 1, is characterized in that, in step (2), the described water-soluble salt containing the first metal is zirconium sulfate, cerous nitrate, magnesium chloride or zinc nitrate;
Described components I is Sodium phosphate dibasic or Sodium hexametaphosphate 99;
Described compositionⅱ is sodium hydroxide or potassium hydroxide.
5. the preparation method of composite coated TiO 2 pigment according to claim 4, is characterized in that, the mole dosage of described components I and compositionⅱ is than being 1:0.1 ~ 5.
6. the preparation method of composite coated TiO 2 pigment according to claim 1, is characterized in that, in step (2), and keeps pH to be 2 ~ 11 when flowing.
7. the preparation method of composite coated TiO 2 pigment according to claim 1, is characterized in that, and the time of flowing is 0.5 ~ 5h.
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|---|---|---|---|
| CN201310086971.8A CN103224717B (en) | 2013-03-18 | 2013-03-18 | Preparation method of composite coating titanium dioxide pigment |
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|---|---|---|---|
| CN201310086971.8A CN103224717B (en) | 2013-03-18 | 2013-03-18 | Preparation method of composite coating titanium dioxide pigment |
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| CN103224717B true CN103224717B (en) | 2015-01-14 |
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| CN103436054B (en) * | 2013-08-29 | 2015-07-01 | 攀钢集团攀枝花钢铁研究院有限公司 | Low viscosity enveloping method of titanium dioxide |
| CN104119702B (en) * | 2014-07-22 | 2015-11-18 | 四川龙蟒钛业股份有限公司 | The zirconium aluminium coating process of a kind of high gloss, high-weatherability Rutile type Titanium Dioxide |
| CN106752109A (en) * | 2016-11-18 | 2017-05-31 | 漯河兴茂钛业股份有限公司 | A kind of preparation method of titanium dioxide used for decorative paper |
| CN106947294A (en) * | 2017-03-14 | 2017-07-14 | 襄阳龙蟒钛业有限公司 | A kind of production method of high fluidity titanium dioxide |
| CN107216687A (en) * | 2017-06-30 | 2017-09-29 | 安徽金星钛白（集团）有限公司 | A kind of method that conductivity type titanium white is prepared based on improvement process of surface treatment |
| CN108997789B (en) * | 2018-09-05 | 2020-11-17 | 攀枝花大互通钛业有限公司 | Composite modified titanium dioxide and preparation method thereof |
| CN111410853B (en) * | 2019-01-05 | 2021-07-06 | 河南佰利联新材料有限公司 | Titanium dioxide pigment and preparation method thereof |
| CN110003687B (en) * | 2019-04-26 | 2021-06-25 | 龙蟒佰利联集团股份有限公司 | Preparation method of special titanium dioxide for high-gloss outdoor coating |
| CN111334093B (en) * | 2020-04-14 | 2021-09-14 | 河南佰利联新材料有限公司 | Titanium dioxide for high-light-resistance laminated paper and preparation method thereof |
| CN112143262A (en) * | 2020-10-09 | 2020-12-29 | 安徽金星钛白（集团）有限公司 | Rare earth composite coated titanium dioxide and preparation method and application thereof |
| CN113563739A (en) * | 2021-07-29 | 2021-10-29 | 安徽金星钛白（集团）有限公司 | Preparation method of composite coated titanium dioxide for bactericidal coating |
| CN114591635B (en) * | 2022-03-04 | 2023-08-11 | 河南佰利联新材料有限公司 | Preparation method of high-weather-resistance high-gloss titanium dioxide |
| CN115490261B (en) * | 2022-10-20 | 2023-11-24 | 福建乐钛科技有限公司 | Titanium dioxide for antibacterial and mildew-proof chemical fiber and preparation method thereof |
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| CN102516825A (en) * | 2011-11-17 | 2012-06-27 | 攀钢集团研究院有限公司 | Continuous inorganic coating method of titanium dioxide |
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| CN102516825A (en) * | 2011-11-17 | 2012-06-27 | 攀钢集团研究院有限公司 | Continuous inorganic coating method of titanium dioxide |
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