CN116924479A - Preparation method of low-conductivity transparent ferric oxide pigment - Google Patents

Preparation method of low-conductivity transparent ferric oxide pigment Download PDF

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CN116924479A
CN116924479A CN202310918017.4A CN202310918017A CN116924479A CN 116924479 A CN116924479 A CN 116924479A CN 202310918017 A CN202310918017 A CN 202310918017A CN 116924479 A CN116924479 A CN 116924479A
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oxide pigment
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iron oxide
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郭玲娟
梁峰
俞军波
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Zhejiang Zhengqi Shirong Technology Co ltd
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    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/22—Compounds of iron
    • C09C1/24—Oxides of iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • C01G49/06—Ferric oxide [Fe2O3]
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    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
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    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
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    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/12—Treatment with organosilicon compounds
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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Abstract

The application relates to the technical field of ferric oxide, and particularly discloses a preparation method of a low-conductivity transparent ferric oxide pigment, which comprises the following steps: s1, adding a crystal form control agent and a sodium hydroxide solution into an iron sulfate solution, adjusting the pH to 8-10, and heating to react to obtain colloid; s2, adding ferric sulfate powder and iron powder into the colloid, heating, stirring for reaction, wherein the pH value of the reaction end point is 4-5, concentrating and washing to obtain slurry; s3, heating the slurry, uniformly stirring, adjusting the pH to 8.5-9, adding a surfactant, continuously heating, and preserving heat to obtain a primary product; s4, pulping and press-filtering the initial product to obtain a filter cake; washing, drying, calcining and crushing the filter cake to obtain ferric oxide pigment; the preparation method disclosed by the application is simple in steps, low in cost and suitable for industrial production, and the obtained ferric oxide pigment is nano-scale, excellent in dispersibility, high in relative tinting strength and transparency, low in conductivity and wide in market prospect.

Description

Preparation method of low-conductivity transparent ferric oxide pigment
Technical Field
The application relates to the technical field of ferric oxide, in particular to a preparation method of a transparent ferric oxide pigment with low conductivity.
Background
The nano ferric oxide as pigment has the characteristics of no toxicity, no smell, weather resistance, ultraviolet resistance, weak acid resistance, alkali resistance and wide color spectrum, and is favored by wide users. The transparency of nano-iron oxide is due to the transmission of visible light; when the particle size of the iron oxide is reduced to 0.1 μm or less, the light transmission is 75% or more of the transmitted light, and a transparent coloring effect is produced, and a transparent state is exhibited. The transparent ferric oxide pigment not only has the performance of common ferric oxide pigment, but also has the advantages of high transparency, bright color when mixed with metal pigment, strong ultraviolet absorption and the like, and is widely applied to the fields of paint, printing ink, plastic products, high-transparency decorative materials, reflective materials, automobile finish paint and the like.
Currently, CN 102838172A discloses a method for preparing nano alpha-Fe 2 O 3 A method of material comprising: (1) To Fe 2+ Adding strong oxidant into the solution to make Fe 2+ Oxidation to Fe 3+ ，Fe 3+ After activation, adding a strong base solution to ph=6.0-11.0 to form Fe (OH) 3 Seed colloid; (2) Heating the seed crystal colloid to 80-90 ℃, and sequentially adding Fe 2+ 、Fe 3+ Gradually growing into nano alpha-FeOOH, wherein the PH of the reaction end point is 3.5-6.0; (3) Filtering and drying the nano alpha-FeOOH, and calcining at 300-400 ℃ to obtain nano alpha-Fe 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the In the preparation process, the growth condition of the crystal forms cannot be well controlled, the mixed crystals are too many, meanwhile, the particle dispersion degree is not high, the phenomenon of easy aggregation occurs, and the application range of the ferric oxide pigment is greatly limited; therefore, there is a need to solve the problems of difficult control of the particle size and shape of the iron oxide and poor dispersibility, so that the iron oxide pigment can better meet the market demands.
Disclosure of Invention
The application provides a preparation method of a low-conductivity transparent ferric oxide pigment, which aims to solve the problems that the particle size and shape of the existing ferric oxide are difficult to control and the dispersibility is poor.
The application provides a preparation method of a low-conductivity transparent ferric oxide pigment, which adopts the following technical scheme:
a method for preparing a transparent iron oxide pigment with low conductivity, comprising the following steps:
s1, preparing colloid: adding a crystal form control agent into the ferric sulfate solution, uniformly stirring, then dropwise adding a sodium hydroxide solution at 35-45 ℃, adjusting the pH to 8-10, heating to 55-64 ℃ for reaction for 4-5h, and obtaining colloid;
s2, preparing slurry: adding ferric sulfate powder and iron powder into the colloid obtained in the step S2, stirring and reacting for 6-8 hours at 82-88 ℃, wherein the pH value of the reaction end point is 4-5, concentrating and washing to obtain slurry;
s3, surface treatment: heating the slurry obtained in the step S2 to 55-65 ℃, uniformly stirring, adjusting the pH to 8.5-9, adding a surfactant, continuously heating to 75-80 ℃, and preserving heat for 0.5-1.5h to obtain a primary product;
s4, removing impurities and purifying: pulping and press-filtering the primary product obtained in the step S3 to obtain a filter cake; washing, drying, calcining and crushing the filter cake to obtain the transparent ferric oxide pigment with low conductivity.
By adopting the technical scheme, in the application, in the step S1, ferric sulfate solution and sodium hydroxide solution react to generate Fe (OH) 3 Colloid seed crystal, crystal form controlling agent and crystal needle structure with excellent dispersivity; in the step S2, ferric sulfate powder and iron powder are added, and the two can undergo oxidation-reduction reaction to generate Fe 2+ While Fe 2+ Can be combined with Fe (OH) 3 Colloid generates alpha-FeOOH particles; in the step S3, a surfactant is added, and hydrophilic and lipophilic surfactants are adsorbed on the surface of the initial product, so that the ferric oxide has better dispersibility in a pigment system; in the impurity removal and purification process of the step S4, the primary product is pulped and filter-pressed, which is favorable for dissolving a large amount of soluble salt in water, removing impurities in ferric oxide, drying, calcining and dehydrating nano alpha-FeOOH to generate alpha-Fe with low conductivity 2 O 3 . In the preparation process of the ferric oxide, the preparation method strictly controls various process parameters, is favorable for crystal growth, and the obtained ferric oxide pigment is nano-scale, has excellent dispersibility, high relative tinting strength and transparency, low conductivity and wide market prospect.
Preferably, the mass of the crystal form control agent is 1-10% of the mass of ferric sulfate in the ferric sulfate solution.
By adopting the technical scheme, the application controls the quality of the crystal form control agent and is beneficial to Fe 3+ With OH - Fully reacts to generate Fe (OH) 3 Colloid seed crystal and control the growth of seed crystal, so that the dispersibility of seed crystal is good.
Preferably, the crystalline form control agent is prepared by the following method:
dissolving chitosan, citric acid, sorbic acid and ionic liquid in water, uniformly stirring, heating to 70-80 ℃, adjusting the pH value to 7-8, and continuously stirring for reacting for 2-5h to obtain the crystal form control agent.
Preferably, the mass ratio of the chitosan, the citric acid, the sorbic acid and the ionic liquid to the water is 10:5-7:4:1-2:80.
By adopting the technical scheme, chitosan, citric acid, sorbic acid and ionic liquid are used as raw materials to prepare the crystal form control agent; chitosan, citric acid, sorbic acid and ionic liquid can be used as ligands to form a complex with iron ions in the solution, so that the morphology of crystals is controlled; the surface active effect can be achieved, the property of a crystal growth interface is changed, and the growth rate and the direction of crystals are influenced; therefore, in the crystal control process, the four components exert synergistic effect and influence each other to jointly regulate the size and uniformity of the alpha-FeOOH crystal, so that the generation of gamma-FeOOH mixed crystal when alpha-FeOOH particles are generated is avoided.
Preferably, the molecular weight of the chitosan is 10-50 ten thousand, and the deacetylation degree is 65-100%.
Preferably, the ionic liquid is prepared by mixing 1-hydroxyethyl-3-methylimidazolamide acetic acid and 1-vinyl-3-ethylimidazole bistrifluoro-methanesulfonimide salt in a mass ratio of 1-4:3.
By adopting the technical scheme, the application takes the 1-hydroxyethyl-3-methylimidazolam glycine and the 1-vinyl-3-ethylimidazole bistrifluoromethanesulfonimide salt as ionic liquids, the two are mutually assisted, and the growth rate and the direction of the alpha-FeOOH crystal can be changed through coordination and surface adsorption; the alpha-FeOOH nano particles can also be used as a wrapping agent to regulate the size and the dispersibility of the alpha-FeOOH nano particles; meanwhile, chemical bonds are combined with chitosan, citric acid and sorbic acid, so that the crystal growth regulation and control performance of the crystal form control agent can be further promoted.
Preferably, the molar ratio of the ferric sulfate powder, the iron powder and the ferric sulfate in the ferric sulfate solution is 0.5:0.16-0.5:1.
By adopting the technical scheme, the application controls the addition amount of the ferric sulfate powder and the iron powder within a certain range to ensure that Fe 3+ Fully reacts with Fe to generate Fe 2+ The phenomenon of excessive iron powder is reduced, and the purity of the iron oxide pigment is further improved.
Preferably, the specific operations of concentration and washing in the step S2 are as follows:
concentrating, washing, secondary concentrating, secondary washing and tertiary concentrating by inclined tube precipitation equipment to obtain slurry.
By adopting the technical scheme, nano-scale particles are difficult to settle in water, and the application adopts inclined tube precipitation equipment, so that the nano-scale particles can be effectively concentrated.
Preferably, the mass of the surfactant is 1-5% of the slurry.
Preferably, the surfactant is prepared by mixing polyvinyl alcohol, polysorbate and gamma-glycidol ether oxypropyl trimethoxysilane in a mass ratio of 4:1-2:1.
By adopting the technical scheme, the application takes the mixture of the polyvinyl alcohol, the polysorbate and the gamma-glycidol ether oxypropyl trimethoxy silane as the surfactant, and the mixing proportion of the polyvinyl alcohol, the polysorbate and the gamma-glycidol ether oxypropyl trimethoxy silane is controlled within a specific range, so that the three are beneficial to coaction, the surface modification and the coating of the generated alpha-FeOOH nano particles are carried out to form a molecular layer, the dispersibility of the alpha-FeOOH nano particles is improved, the compatibility between the ferric oxide pigment and other pigments is further improved, and the agglomeration phenomenon of pigment particles is effectively prevented.
Preferably, the beating conditions are as follows: adding water 3-5 times of the mass of the primary product, rotating at 5000-20000rpm for 0.5-3min at 5-10deg.C.
Preferably, the filter pressing adopts a membrane filter press, and the conditions are as follows: the pressure is 0.8-1Mpa, and the dwell time is 10-20min.
Preferably, the drying is spray drying, and the condition is that the inlet air temperature is 160-200 ℃ and the outlet air temperature is 70-90 ℃.
In summary, the application has the following beneficial effects:
1. in the process of preparing transparent ferric oxide, the method is mainly divided into four steps, namely, firstly, a crystal form control agent and a sodium hydroxide solution are added into an ferric sulfate solution to generate colloid; adding ferric sulfate powder and iron powder into the colloid, and continuing to react to obtain slurry; adding a surfactant into the slurry, and uniformly stirring to obtain a primary product; finally removing impurities and purifying to obtain the low-conductivity transparent ferric oxide pigment; the preparation method provided by the application has the advantages of simple steps, low cost and suitability for industrial production, and the obtained ferric oxide pigment is nano-scale, low in conductivity, good in dispersibility and wide in market prospect.
2. The crystal form control agent is prepared from chitosan, citric acid, sorbic acid and ionic liquid serving as raw materials, wherein the ionic liquid is prepared by mixing 1-hydroxyethyl-3-methylimidazolam-glycine and 1-vinyl-3-ethylimidazole bistrifluoromethanesulfonimide salt, and the substances interact with each other, so that the obtained crystal form control agent can effectively control the particle size shape of ferric oxide, and is more beneficial to the formation of alpha-type crystals; meanwhile, the surfactant is a mixture of polyvinyl alcohol, polysorbate and gamma-glycidol ether oxypropyl trimethoxy silane, and the three are synergistic, so that the dispersibility of the ferric oxide pigment is effectively improved.
Detailed Description
The present application will be described in further detail with reference to examples.
Preparation examples 1 to 5 and comparative preparation examples 1 to 6 provide a preparation method of the crystalline form control agent.
Preparation example 1
A crystalline form control agent prepared by the method of:
dissolving 10g of chitosan, 5g of citric acid, 4g of sorbic acid and 1g of ionic liquid in 80g of water, stirring for 10min at the rotating speed of 200r/min, heating to 70 ℃ after uniform mixing, adjusting the pH value to 7, keeping the same rotating speed, and stirring for 2h to obtain a crystal form control agent;
wherein, the molecular weight of the chitosan is 10 ten thousand, and the deacetylation degree is 65%; the ionic liquid is prepared by mixing 1-hydroxyethyl-3-methylimidazolam glycine and 1-vinyl-3-ethylimidazole bistrifluoro methanesulfonimide salt in a mass ratio of 1:3.
Preparation example 2
A crystalline form control agent prepared by the method of:
dissolving 10g of chitosan, 5.5g of citric acid, 4g of sorbic acid and 1.2g of ionic liquid in 80g of water, stirring for 12min at the rotating speed of 250r/min, heating to 72 ℃ after uniform mixing, adjusting the pH value to 7.2, keeping the same rotating speed, and stirring and reacting for 2.5h to obtain a crystal form control agent;
wherein, the molecular weight of the chitosan is 20 ten thousand, and the deacetylation degree is 70%; the ionic liquid is prepared by mixing 1-hydroxyethyl-3-methylimidazolam glycine and 1-vinyl-3-ethylimidazole bistrifluoro methanesulfonimide salt in a mass ratio of 2:3.
Preparation example 3
A crystalline form control agent prepared by the method of:
dissolving 10g of chitosan, 6g of citric acid, 4g of sorbic acid and 1.5g of ionic liquid in 80g of water, stirring for 15min at the rotating speed of 300r/min, heating to 75 ℃ after uniform mixing, adjusting the pH value to 7.5, keeping the same rotating speed, and stirring for 3h to obtain a crystal form control agent;
wherein, the molecular weight of the chitosan is 3 ten thousand, and the deacetylation degree is 80%; the ionic liquid is prepared by mixing 1-hydroxyethyl-3-methylimidazolam glycine and 1-vinyl-3-ethylimidazole bistrifluoro methanesulfonimide salt in a mass ratio of 2.5:3.
Preparation example 4
A crystalline form control agent prepared by the method of:
dissolving 10g of chitosan, 6.5g of citric acid, 4g of sorbic acid and 1.8g of ionic liquid in 80g of water, stirring for 18min at the rotating speed of 350r/min, heating to 78 ℃ after uniform mixing, adjusting the pH value to 7.8, keeping the same rotating speed, and stirring and reacting for 4h to obtain a crystal form control agent;
wherein, the molecular weight of the chitosan is 40 ten thousand, and the deacetylation degree is 90%; the ionic liquid is prepared by mixing 1-hydroxyethyl-3-methylimidazolam glycine and 1-vinyl-3-ethylimidazole bistrifluoro methanesulfonimide salt in a mass ratio of 1:1.
Preparation example 5
A crystalline form control agent prepared by the method of:
dissolving 10g of chitosan, 7g of citric acid, 4g of sorbic acid and 2g of ionic liquid in 80g of water, stirring for 20min at the rotation speed of 400r/min, heating to 80 ℃ after uniform mixing, adjusting the pH value to 8, keeping the same rotation speed, and stirring for reacting for 5h to obtain a crystal form control agent;
wherein, the molecular weight of the chitosan is 50 ten thousand, and the deacetylation degree is 100%; the ionic liquid is prepared by mixing 1-hydroxyethyl-3-methylimidazolam glycine and 1-vinyl-3-ethylimidazole bistrifluoro methanesulfonimide salt in a mass ratio of 4:3.
Comparative preparation example 1
Comparative preparation 1 differs from preparation 1 only in that: no chitosan was added.
Comparative preparation example 2
Comparative preparation 2 differs from preparation 1 only in that: no citric acid was added.
Comparative preparation example 3
Comparative preparation 3 differs from preparation 1 only in that: no sorbic acid was added.
Comparative preparation example 4
Comparative preparation 4 differs from preparation 1 only in that: no ionic liquid was added.
Comparative preparation example 5
Comparative preparation 5 differs from preparation 1 only in that: the ionic liquid is only 1-hydroxyethyl-3-methylimidazolam-acetic acid.
Comparative preparation example 6
Comparative preparation 6 differs from preparation 1 only in that: the ionic liquid is only 1-vinyl-3-ethylimidazole bistrifluoromethanesulfonimide salt.
Examples 1-5 provide a method for preparing a low conductivity transparent iron oxide pigment.
Example 1
A method for preparing a transparent iron oxide pigment with low conductivity, comprising the following steps:
s1, preparing colloid: adding 4g of crystal form control agent into 1000L of 1mol/L ferric sulfate solution, stirring for 10min at the rotating speed of 200r/min, uniformly mixing, then dropwise adding 1mol/L sodium hydroxide solution at 35 ℃, regulating the pH value to 8, and heating to 55 ℃ for reaction for 4h to obtain colloid;
wherein, the crystal form control agent is prepared in preparation example 1;
s2, preparing slurry: adding 0.5mol of ferric sulfate powder and 0.16mol of iron powder into the colloid obtained in the step S2, stirring and reacting for 6 hours at the temperature of 82 ℃ at the rotating speed of 200r/min, wherein the pH value of the reaction end point is 4; then concentrating, washing, secondary concentrating, secondary washing and tertiary concentrating are sequentially carried out by inclined tube precipitation equipment to obtain slurry;
s3, surface treatment: heating the slurry obtained in the step S2 to 55 ℃, stirring at the rotation speed of 400r/min, regulating the pH value to 8.5, adding a surfactant accounting for 1% of the mass of the slurry, continuously heating to 75 ℃, and preserving heat for 0.5h to obtain a primary product;
wherein the surfactant is prepared by mixing polyvinyl alcohol, polysorbate and gamma-glycidol ether oxypropyl trimethoxy silane in a mass ratio of 4:1:1;
s4, removing impurities and purifying: pulping the primary product obtained in the step S3, adding water with the mass 3 times of that of the primary product, rotating at 5000rpm for 0.5min and at 5 ℃; then press-filtering in a membrane press filter, and maintaining the pressure for 10min under 0.8Mpa to obtain a filter cake; washing the filter cake with water, spray drying at 160deg.C for inlet air and 70deg.C for outlet air, calcining at 220deg.C, and pulverizing to obtain transparent ferric oxide pigment with low conductivity.
Example 2
A method for preparing a transparent iron oxide pigment with low conductivity, comprising the following steps:
s1, preparing colloid: adding 10g of crystal form control agent into 1000L of 1mol/L ferric sulfate solution, stirring for 12min at the rotating speed of 300r/min, dripping 1mol/L sodium hydroxide solution at 38 ℃ after uniformly mixing, regulating the pH value to 8.5, and heating to 58 ℃ for reacting for 4.2h to obtain colloid;
wherein, the crystal form control agent is prepared in preparation example 2;
s2, preparing slurry: adding 0.5mol of ferric sulfate powder and 0.2mol of iron powder into the colloid obtained in the step S2, stirring at the speed of 300r/min at 84 ℃ for reaction for 6.5 hours, wherein the pH value of the reaction end point is 4.2; then concentrating, washing, secondary concentrating, secondary washing and tertiary concentrating are sequentially carried out by inclined tube precipitation equipment to obtain slurry;
s3, surface treatment: heating the slurry obtained in the step S2 to 58 ℃, stirring at the rotating speed of 500r/min, regulating the pH value to 8.6, adding a surfactant accounting for 2% of the mass of the slurry, continuously heating to 77 ℃, and preserving heat for 0.8h to obtain a primary product;
wherein the surfactant is prepared by mixing polyvinyl alcohol, polysorbate and gamma-glycidol ether oxypropyl trimethoxy silane in a mass ratio of 4:1.2:1;
s4, removing impurities and purifying: pulping the primary product obtained in the step S3, adding water with the mass 3.5 times of that of the primary product, and rotating at 8000rpm for 1min at 6 ℃; then press-filtering in a membrane press filter, and maintaining the pressure for 11min under 0.85Mpa to obtain a filter cake; washing the filter cake with water, spray drying at 170 deg.C and 72 deg.C, calcining at 230 deg.C, and pulverizing to obtain transparent iron oxide pigment with low conductivity.
Example 3
A method for preparing a transparent iron oxide pigment with low conductivity, comprising the following steps:
s1, preparing colloid: adding 20g of crystal form control agent into 1000L of 1mol/L ferric sulfate solution, stirring for 15min at the rotating speed of 400r/min, dripping 1mol/L sodium hydroxide solution at 40 ℃ after uniformly mixing, regulating the pH value to 9, and heating to 60 ℃ for reaction for 4.5h to obtain colloid;
wherein, the crystal form control agent is prepared in preparation example 3;
s2, preparing slurry: adding 0.5mol of ferric sulfate powder and 0.3mol of iron powder into the colloid obtained in the step S2, stirring at 86 ℃ and a rotating speed of 40r/min for reaction for 7 hours, wherein the pH value of the reaction end point is 4.5; then concentrating, washing, secondary concentrating, secondary washing and tertiary concentrating are sequentially carried out by inclined tube precipitation equipment to obtain slurry;
s3, surface treatment: heating the slurry obtained in the step S2 to 60 ℃, stirring at the rotating speed of 600r/min, adjusting the pH value to 8.8, adding a surfactant accounting for 3% of the mass of the slurry, continuously heating to 88 ℃, and preserving heat for 1h to obtain a primary product;
wherein the surfactant is prepared by mixing polyvinyl alcohol, polysorbate and gamma-glycidol ether oxypropyl trimethoxy silane in a mass ratio of 4:1.5:1;
s4, removing impurities and purifying: pulping the primary product obtained in the step S3, adding water with the mass 3-5 times of that of the primary product, wherein the rotating speed is 15000rpm, the time is 2min, and the temperature is 8 ℃; then press-filtering in a membrane press filter, and maintaining the pressure for 15min under 0.9Mpa to obtain a filter cake; washing the filter cake with water, spray drying at 180 deg.C for air inlet and 80 deg.C for air outlet, calcining at 240 deg.C, and pulverizing to obtain transparent iron oxide pigment with low conductivity.
Example 4
A method for preparing a transparent iron oxide pigment with low conductivity, comprising the following steps:
s1, preparing colloid: adding 30g of crystal form control agent into 1000L of 1mol/L ferric sulfate solution, stirring for 18min at the rotating speed of 500r/min, uniformly mixing, then dropwise adding 1mol/L sodium hydroxide solution at 42 ℃, adjusting the pH value to 9.5, and heating to 62 ℃ for reacting for 4.8h to obtain colloid;
wherein, the crystal form control agent is prepared in preparation example 4;
s2, preparing slurry: adding 0.5mol of ferric sulfate powder and 0.4mol of iron powder into the colloid obtained in the step S2, stirring at the speed of 500r/min at 87 ℃ for reaction for 7.5 hours, wherein the pH value of the reaction end point is 4.8; then concentrating, washing, secondary concentrating, secondary washing and tertiary concentrating are sequentially carried out by inclined tube precipitation equipment to obtain slurry;
s3, surface treatment: heating the slurry obtained in the step S2 to 62 ℃, stirring at the rotating speed of 700r/min, adjusting the pH value to 8.9, adding a surfactant accounting for 4% of the mass of the slurry, continuously heating to 79 ℃, and preserving heat for 1.2h to obtain a primary product;
wherein the surfactant is prepared by mixing polyvinyl alcohol, polysorbate and gamma-glycidol ether oxypropyl trimethoxy silane in a mass ratio of 4:1.8:1;
s4, removing impurities and purifying: pulping the primary product obtained in the step S3, adding water with the mass 4.5 times of that of the primary product, and rotating at 18000rpm for 2.5min at 8 ℃; then press-filtering in a membrane press filter, and maintaining the pressure for 18min under 0.95Mpa to obtain a filter cake; washing the filter cake with water, spray drying at 190 deg.C and 85 deg.C, calcining at 250 deg.C, and pulverizing to 350 mesh to obtain the final product.
Example 5
A method for preparing a transparent iron oxide pigment with low conductivity, comprising the following steps:
s1, preparing colloid: adding 40g of crystal form control agent into 1000L of 1mol/L ferric sulfate solution, stirring for 20min at the rotating speed of 600r/min, dripping 1mol/L sodium hydroxide solution at 45 ℃ after uniformly mixing, regulating the pH value to 10, and heating to 64 ℃ for reacting for 5h to obtain colloid;
wherein, the crystal form control agent is prepared in preparation example 5;
s2, preparing slurry: adding 0.5mol of ferric sulfate powder and 0.5mol of iron powder into the colloid obtained in the step S2, stirring at 88 ℃ at the rotating speed of 600r/min for reaction for 8 hours, wherein the pH value of the reaction end point is 5; then concentrating, washing, secondary concentrating, secondary washing and tertiary concentrating are sequentially carried out by inclined tube precipitation equipment to obtain slurry;
s3, surface treatment: heating the slurry obtained in the step S2 to 65 ℃, stirring at the rotating speed of 800r/min, adjusting the pH value to 9, adding a surfactant accounting for 1-5% of the mass of the slurry, continuously heating to 80 ℃, and preserving heat for 1.5h to obtain a primary product;
wherein the surfactant is prepared by mixing polyvinyl alcohol, polysorbate and gamma-glycidol ether oxypropyl trimethoxy silane in a mass ratio of 4:2:1;
s4, removing impurities and purifying: pulping the primary product obtained in the step S3, adding water with the mass 5 times of that of the primary product, rotating at 20000rpm for 3min at the temperature of 10 ℃; then press-filtering in a membrane press filter, and maintaining the pressure for 20min under 1Mpa to obtain a filter cake; washing the filter cake with water, spray drying at air inlet temperature of 200deg.C and air outlet temperature of 90deg.C, calcining at 260 deg.C, and pulverizing to obtain transparent ferric oxide pigment with low conductivity.
To verify the performance of the iron oxide pigments provided by the present application, the applicant set comparative examples 1 to 11, in which:
comparative example 1
Comparative example 1 differs from example 1 only in that: the crystalline form control agent was prepared from comparative preparation 1.
Comparative example 2
Comparative example 2 differs from example 1 only in that: the crystalline form control agent was prepared from comparative preparation 2.
Comparative example 3
Comparative example 3 differs from example 1 only in that: the crystalline form control agent was prepared from comparative preparation 3.
Comparative example 4
Comparative example 4 differs from example 1 only in that: the crystalline form control agent was prepared from comparative preparation 4.
Comparative example 5
Comparative example 5 differs from example 1 only in that: the crystalline form control agent was prepared from comparative preparation 5.
Comparative example 6
Comparative example 6 differs from example 1 only in that: the crystalline form control agent was prepared from comparative preparation 6.
Comparative example 7
Comparative example 7 differs from example 1 only in that: no crystal form control agent was added.
Comparative example 8
Comparative example 8 differs from example 1 only in that: the surfactant is prepared by mixing polyvinyl alcohol and polysorbate in a mass ratio of 4:1.
Comparative example 9
Comparative example 9 differs from example 1 only in that: the surfactant is prepared by mixing polyvinyl alcohol and gamma-glycidol ether oxypropyl trimethoxy silane in a mass ratio of 4:1.
Comparative example 10
Comparative example 10 differs from example 1 only in that: the surfactant is prepared by mixing polysorbate and gamma-glycidol ether oxypropyl trimethoxy silane in a mass ratio of 1:1.
Comparative example 11
Comparative example 11 differs from example 1 only in that: the specific operation of step S3 is not performed, and the slurry obtained in step S2 is directly subjected to the impurity removal and purification treatment of step S4.
The main properties of the iron oxide pigments of examples 1-5 and comparative examples 1-11, respectively, were tested to give the following result parameters, see in particular Table 1:
particle size: the particle size of the ferric oxide is tested by adopting a laser particle sizer, the testing method is a wet method, the shading rate for testing is 5-20%, and the testing medium is water; respectively measuring the medium particle diameters D50 and D90;
conductivity: pressing ferric oxide into a circular sheet with the diameter of 10mm and the thickness of 1-2mm, and then using a four-probe tester to test the conductivity of the block;
zeta potential: measuring the Zeta potential of the ferric oxide in the deionized water by adopting a Malvern Zetasizer Nano series granularity-potentiometer; tinting strength: the relative tinting strength of the iron oxide was tested according to HG/T3951-2007 appendix B.
Table 1:
as can be seen from the data shown in table 1: the iron oxide pigment obtained in the examples 1-5 of the application has the comprehensive performance far superior to that of the transparent iron oxide pigment with low conductivity obtained in the comparative examples 1-11, has small particle size, low conductivity, good dispersibility, high tinting strength and wide application prospect.
From example 1 and comparative examples 1 to 4, 7, it is understood that: in the embodiment 1, the crystal form control agent is added, and the crystal form control agent is prepared from the preparation example 1, wherein the preparation example 1 is prepared from chitosan, citric acid, sorbic acid and ionic liquid as raw materials, compared with the iron oxide pigment obtained in the comparison examples 1-4 and 7, the particle size of the iron oxide pigment obtained in the embodiment 1 is smaller, the conductivity is lower, the dispersion is more uniform, the crystal form control agent is fully described to be favorable for the growth of alpha-FeOOH crystals, and the chitosan, the citric acid, the sorbic acid and the ionic liquid are combined to cooperatively regulate the size and the uniformity of the alpha-FeOOH crystals.
As can be seen from example 1 and comparative examples 5 and 6: the crystalline form control agent in example 1 was prepared from preparation example 1, and the ionic liquid was obtained by mixing 1-hydroxyethyl-3-methylimidazolamide acetic acid and 1-vinyl-3-ethylimidazole bistrifluoromethanesulfonimide salt, and compared with comparative examples 5 and 6, the conductivity of the iron oxide pigment obtained in example 1 was lower, indicating that the mixture of 1-hydroxyethyl-3-methylimidazolamide acetic acid and 1-vinyl-3-ethylimidazole bistrifluoromethanesulfonimide salt was used as the ionic liquid, which was more conducive to the growth of α -FeOOH crystals.
From example 1 and comparative examples 8 to 11, it can be seen that: in example 1, a surfactant is added, and the surfactant is a mixture of polyvinyl alcohol, polysorbate and gamma-glycidoxypropyl trimethoxysilane, and compared with comparative examples 8-11, the dispersibility and tinting strength of the iron oxide pigment obtained in example 1 are higher, so that the surface of the iron oxide is fully modified by the surfactant, the dispersibility of the iron oxide is improved, and the dispersibility of the iron oxide pigment is further improved by using the mixture of polyvinyl alcohol, polysorbate and gamma-glycidoxypropyl trimethoxysilane as the surfactant.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.

Claims (10)

1. A method for preparing a transparent iron oxide pigment with low conductivity, which is characterized by comprising the following steps:
s1, preparing colloid: adding a crystal form control agent into the ferric sulfate solution, uniformly stirring, then dropwise adding a sodium hydroxide solution at 35-45 ℃, adjusting the pH to 8-10, heating to 55-64 ℃ for reaction for 4-5h, and obtaining colloid;
s2, preparing slurry: adding ferric sulfate powder and iron powder into the colloid obtained in the step S2, stirring and reacting for 6-8 hours at 82-88 ℃, wherein the pH value of the reaction end point is 4-5, concentrating and washing to obtain slurry;
s3, surface treatment: heating the slurry obtained in the step S2 to 55-65 ℃, uniformly stirring, adjusting the pH to 8.5-9, adding a surfactant, continuously heating to 75-80 ℃, and preserving heat for 0.5-1.5h to obtain a primary product;
s4, removing impurities and purifying: pulping and press-filtering the primary product obtained in the step S3 to obtain a filter cake; washing, drying, calcining and crushing the filter cake to obtain the transparent ferric oxide pigment with low conductivity.
2. The method for preparing a transparent iron oxide pigment having low conductivity according to claim 1, wherein the mass of the crystal form controlling agent is 1 to 10% of the mass of iron sulfate in the iron sulfate solution.
3. The method for preparing a low-conductivity transparent iron oxide pigment according to claim 1, wherein the crystal form control agent is prepared by the following method:
dissolving chitosan, citric acid, sorbic acid and ionic liquid in water, uniformly stirring, heating to 70-80 ℃, adjusting the pH value to 7-8, and continuously stirring for reacting for 2-5h to obtain the crystal form control agent.
4. The method for preparing a transparent iron oxide pigment with low conductivity according to claim 3, wherein the mass ratio of chitosan, citric acid, sorbic acid, ionic liquid and water is 10:5-7:4:1-2:80.
5. The method for preparing a transparent iron oxide pigment with low conductivity according to claim 3, wherein the ionic liquid is obtained by mixing 1-hydroxyethyl-3-methylimidazolam-based acetic acid and 1-vinyl-3-ethylimidazole bistrifluoromethanesulfonimide salt in a mass ratio of 1-4:3.
6. The method for preparing a transparent iron oxide pigment having low conductivity according to claim 1, wherein the molar ratio of the iron sulfate powder, the iron powder and the iron sulfate in the iron sulfate solution is 0.5:0.16-0.5:1.
7. The method for preparing a transparent iron oxide pigment having low conductivity according to claim 1, wherein the mass of the surfactant is 1 to 5% of the slurry.
8. The method for preparing a transparent iron oxide pigment with low conductivity according to claim 7, wherein the surfactant is prepared by mixing polyvinyl alcohol, polysorbate and gamma-glycidoxypropyl trimethoxysilane in a mass ratio of 4:1-2:1.
9. The method for preparing a low-conductivity transparent iron oxide pigment according to claim 1, wherein the beating conditions are: adding water 3-5 times of the mass of the primary product, rotating at 5000-20000rpm for 0.5-3min at 5-10deg.C.
10. The method for preparing a transparent iron oxide pigment with low conductivity according to claim 1, wherein the filter pressing adopts a membrane filter press, provided that: the pressure is 0.8-1Mpa, and the dwell time is 10-20min.
CN202310918017.4A 2023-07-25 2023-07-25 Preparation method of low-conductivity transparent ferric oxide pigment Pending CN116924479A (en)

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