CN107858014B - Preparation method of organic mesochrome with core-shell structure - Google Patents

Preparation method of organic mesochrome with core-shell structure Download PDF

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CN107858014B
CN107858014B CN201710930228.4A CN201710930228A CN107858014B CN 107858014 B CN107858014 B CN 107858014B CN 201710930228 A CN201710930228 A CN 201710930228A CN 107858014 B CN107858014 B CN 107858014B
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water
organic
yellow
pss
pah
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CN107858014A (en
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冯伟仁
龚观军
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Hangzhou Qianjin Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0001—Post-treatment of organic pigments or dyes
    • C09B67/0004—Coated particulate pigments or dyes
    • C09B67/0007—Coated particulate pigments or dyes with inorganic coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0001—Post-treatment of organic pigments or dyes
    • C09B67/0002—Grinding; Milling with solid grinding or milling assistants

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)

Abstract

The invention provides a preparation method of organic mesogen yellow with a core-shell structure, which comprises the steps of firstly adsorbing a plurality of layers of polyelectrolyte on the surface of the organic mesogen yellow, and then coating a layer of SiO on the surface of the organic mesogen yellow by adopting a sol-gel method2(ii) a On the basis, a layer of 5-20 nm SiO is adsorbed again2Nanoparticles prepared to have two layers of SiO2Coated organic medium yellow pigment particles. The invention adopts a method of twice coating to prepare SiO2The surface of the shell layer is rough, so that the wettability of the product to water is greatly improved, and the dispersing capacity of the organic mesochrome in water is improved.

Description

Preparation method of organic mesochrome with core-shell structure
Technical Field
The invention relates to a preparation method of organic medium yellow with a core-shell structure, belonging to the field of organic pigments.
Background
The organic medium yellow is an excellent environment-friendly organic pigment. Its color is close to medium chrome yellow, colouring power is strong, alkali resistance is good, it contains no lead, and it is non-toxic, and can be extensively used in paint, printing ink and cultural and educational articles. But it has poor solvent and heat resistance. With the enhancement of people's consciousness on environmental protection, a series of novel products such as water-based ink, water-based paint and the like which take water as a disperse phase appear instead of organic matters as solvents. Organic mesochrome has poor dispersibility in an aqueous phase and is easy to agglomerate, so that various methods are continuously searched for improving the dispersibility of the organic mesochrome in water, wherein surface modification treatment is an important means.
The composite material with the core-shell structure can be designed according to different properties of the core and the shell according to the requirements of people, and has become a research hotspot in recent years. The basic principle of a core-shell structure is utilized to carry out coating treatment on the organic medium yellow, so that the solvent resistance and heat resistance of the organic medium yellow can be improved, and a shell substance with hydrophilic property can be selected to improve the wettability of the organic medium yellow pigment to water, thereby improving the dispersion capability of the pigment in a water phase.
Disclosure of Invention
The invention provides a preparation method of organic yellow with a core-shell structure, which takes organic yellow as a core and adopts the steps of tetraethyl silicate (TEOS) hydrolysis and SiO2The nano particles are adsorbed for two times of coating treatment, and a layer of SiO with rough surface is prepared on the surface of the pigment particles2A shell layer, which is used for improving the dispersibility of the organic medium yellow in water. In order to achieve the technical effects, the invention comprises the following technical steps:
step 1: preparing pigment color paste, namely weighing a certain amount of sodium polystyrene sulfonate Powder (PSS), adding the PSS into deionized water to dissolve the PSS, then adding organic medium yellow powder, stirring the powder to be fully wetted, putting zirconia steel balls into the powder, and grinding the powder in a grinding machine to prepare the uniformly dispersed organic medium yellow pigment particle color paste;
step 2: and (3) carrying out surface treatment on the pigment particles, centrifugally separating the pigment paste, washing the pigment paste for three times by using deionized water, and then dispersing the pigment paste into the deionized water, wherein the surfaces of the pigment particles are negatively charged. Adding a polyallylammonium hydrochloride (PAH) solution into a pigment particle dispersion liquid, performing ultrasonic dispersion for 30min, performing centrifugal separation, and washing with deionized water for three times, wherein the surface of the pigment particle is positively charged; repeating the steps to prepare pigment particles with surfaces alternately adsorbing multiple layers of PSS-PAH polyelectrolytes and positively charged;
and step 3: coating pigment particles for one time, dispersing the pigment particles with positive electricity on the surface into an ethanol solution, adding a proper amount of water, gradually adding ammonia water under the stirring condition to adjust the pH value of the solution to 9-10, and then dropwise adding a mixed solution of tetraethyl silicate (TEOS) and ethanol within 1 hour; then, continuously stirring for 24 hours at room temperature, washing with water and centrifuging for three times to obtain primary coated organic pigment particles;
and 4, step 4: dispersing the primary coated pigment particles in water, adding polyallylammonium hydrochloride (PAH), ultrasonically dispersing for 30min, and then washing and centrifuging for 3 times; dispersing the washed and centrifuged pigment particles in water, then adding nano silica sol with the particle size of 5-20 nm, stirring and adsorbing for 60min, washing and centrifuging for three times by using water to obtain secondarily coated pigment particles, and drying to obtain the organic seed yellow with the core-shell structure.
Furthermore, in the step 1, the feeding ratio of organic medium yellow, PSS and water is mOrganic medium yellow：mPSS：mWater (W)＝0.5～1:0.5～1:100。
Furthermore, in the step 2, the feeding ratio of organic medium yellow, PAH, PSS and water is mOrganic medium yellow：mPAH：mPSS：mWater (W)The ratio of the PSS-PAH polyelectrolyte to the surface treatment agent is 0.5-1: 100, and the number of the adsorption layers of the surface treatment PSS-PAH polyelectrolyte is 3-6. Because the surface of the pigment particles is generally inert, the adsorption capacity to polyelectrolyte is weak, and the adsorption amount of a monolayer is small, so that the subsequent coating treatment is not facilitated.
Furthermore, in the step 3, the feeding ratio of the organic medium yellow to the absolute ethyl alcohol to the water to the TEOS ethyl alcohol solution is mOrganic medium yellow：mAnhydrous ethanol：mWater (W)：mTEOS ethanol solutionThe mass concentration of the absolute ethyl alcohol solution of TEOS is 2-5 percent, wherein the ratio of TEOS to TEOS is 0.5:200: 20-30: 40. During the preparation process, the hydrolysis speed of TEOS can be controlled by changing the quality of water in the system, and SiO can be adjusted by changing the concentration of TEOS solution2The thickness of the coating.
Further, in the step 4, the feeding ratio of organic mesogen yellow, water, PAH and nano silica sol is mOrganic medium yellow：mWater (W)：mPAH：mSiO2＝1:100:1:1～2。
Furthermore, the second layer of coating in the step 4 can increase the coating of SiO on the surface of the organic medium yellow pigment particles2Thereby increasing the stability of the shell; on the other hand 20nm SiO2The particles are adsorbed on the SiO prepared by secondary hydrolysis in the first coating2The surface of the film can improve the SiO of the surface2The roughness of the core-shell structure can further improve the water wettability of the organic medium yellow of the core-shell structure.
Based on the above, the invention provides a preparation method of organic seed yellow with a core-shell structure, which comprises the steps of firstly adsorbing multiple layers of polyelectrolyte on the surface of the organic seed yellow, and then coating a layer of SiO on the surface of the organic seed yellow by adopting a sol-gel method2(ii) a On the basis of whichAdsorbing a layer of 5-20 nm SiO again2Nanoparticles prepared to have two layers of SiO2Coated organic seed yellow pigment particles. SiO prepared by adopting two-time coating2The surface of the shell layer is rough, so that the wettability of the product to water is greatly improved, and the dispersing capacity of the organic mesochrome in water is improved.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
Example 1
The preparation method of the organic seed yellow with the core-shell structure comprises the following steps:
step 1: preparing pigment color paste, namely weighing 0.5g of sodium polystyrene sulfonate Powder (PSS), adding the sodium polystyrene sulfonate Powder (PSS) into 100g of deionized water to dissolve the PSS, then adding 0.5g of organic medium yellow powder, stirring the powder to be fully wetted, putting zirconia steel balls into the mixture, and grinding the mixture in a grinding machine to obtain the uniformly dispersed organic medium yellow pigment color paste;
step 2: and (3) carrying out surface treatment on the pigment particles, namely centrifugally separating the pigment paste, washing the pigment paste for three times by using deionized water, and then dispersing the pigment paste into 100g of deionized water, wherein the surfaces of the pigment particles are negatively charged. 0.5g of polyallylammonium hydrochloride (PAH) solution was added to the pigment particle dispersion, ultrasonically dispersed for 30min, centrifugally separated, and washed three times with deionized water, at which time the pigment particle surface was positively charged. Repeating the steps to prepare pigment particles with surfaces alternately adsorbing 3 layers of PSS-PAH polyelectrolyte and positively charged;
and step 3: coating pigment particles for one time, dispersing the pigment yellow particles in the step 2 into 100g of ethanol solution, adding a proper amount of 10g of water, gradually adding ammonia water under stirring to adjust the pH value of the solution to be 9-10, and then dropwise adding 20g of tetraethyl silicate (TEOS) ethanol solution with the mass fraction of 2.5% within 1 hour; then, continuously stirring for 24 hours at room temperature, washing with water and centrifuging for three times to obtain primary coated organic pigment particles;
and 4, step 4: dispersing the primary coated pigment particles in water, adding 0.5g of polyallylammonium hydrochloride (PAH) solution, ultrasonically dispersing for 30min, and then washing with water and centrifuging for three times; dispersing the centrifugally washed pigment particles into 50g of water, then adding 2.5g of silica sol with the mass fraction of 20% and the particle size of 20nm, magnetically stirring and adsorbing for 60min, washing and centrifuging for three times by using water to obtain secondarily coated pigment particles, and drying to obtain the organic seed yellow with the core-shell structure.
Example 2
The preparation method of the organic seed yellow with the core-shell structure comprises the following steps:
step 1: preparing pigment color paste, namely weighing 0.5g of sodium polystyrene sulfonate Powder (PSS), adding the sodium polystyrene sulfonate Powder (PSS) into 100g of deionized water to dissolve the PSS, then adding 0.5g of organic medium yellow powder, stirring the powder to be fully wetted, putting zirconia steel balls into the mixture, and grinding the mixture in a grinding machine to obtain the uniformly dispersed organic medium yellow pigment color paste;
step 2: carrying out surface treatment on pigment particles, namely centrifugally separating the pigment paste, washing the pigment paste for three times by using deionized water, and then dispersing the pigment paste into 100g of deionized water, wherein the surfaces of the pigment particles are negatively charged; adding 0.5g of polyallylammonium hydrochloride (PAH) solution into the pigment particle dispersion liquid, carrying out ultrasonic dispersion for 30min, carrying out centrifugal separation, and washing with deionized water for three times, wherein the surface of the pigment particles is positively charged; repeating the steps to prepare pigment particles with surfaces alternately adsorbing 3 layers of PSS-PAH polyelectrolyte and positively charged;
and step 3: coating pigment particles for one time, dispersing the pigment yellow particles in the step 2 into 100g of ethanol solution, adding a proper amount of 10g of water, gradually adding ammonia water under stirring to adjust the pH value of the solution to be 9-10, and then dropwise adding 20g of tetraethyl silicate (TEOS) ethanol solution with the mass fraction of 2.5% within 1 hour; then, continuously stirring for 24 hours at room temperature, washing with water and centrifuging for three times to obtain primary coated organic pigment particles;
and 4, step 4: dispersing the primary coated pigment particles in water, adding 0.5g of polyallylammonium hydrochloride (PAH) solution, ultrasonically dispersing for 30min, and then washing with water and centrifuging for 3 times; dispersing the centrifugally washed pigment particles into 50g of water, then adding 2.5g of silica sol with the mass fraction of 20% and the particle size of 5-7 nm, magnetically stirring and adsorbing for 60min, washing and centrifuging for three times by using water to obtain secondarily coated pigment particles, and drying to obtain the organic seed yellow with the core-shell structure.
Untreated organic seed yellow and the samples prepared in the examples were dried, pressed into disks with a tablet press and then measured for water contact angle measurements, respectively, with the results shown in the following table:
sample (I) Untreated organic medium yellow Example 1 Example 2
Contact angle 108.9° 13.2° 5.1°
The data in the table show that the contact angle of the sample prepared in the example to water is greatly reduced, which indicates that the organic mesogen is well coated by the silicon dioxide, so that the water wettability of the organic mesogen is improved. Among these, the contact angle of the sample of example 2 is smaller than that of example 1 because of the sol SiO at the time of secondary coating used in example 22The particle size of the prepared sample is smaller, and the shell layer of the prepared sample is rougher, so that the wetting property to water is better. Therefore, the organic mesoyellow with the core-shell structure prepared in the example can be better dispersed in water.
In the above embodiments, the present invention is described in detail, but the present invention is not limited to the contents of the embodiments. For the person skilled in the art, modifications can be made to the invention without departing from the basic idea of the invention, which is defined in the claims.

Claims (5)

1. A preparation method of organic mesogen-yellow with a core-shell structure is characterized by comprising the following steps:
step 1: preparing pigment color paste, namely weighing a certain amount of sodium polystyrene sulfonate Powder (PSS), adding the sodium polystyrene sulfonate Powder (PSS) into deionized water to dissolve the PSS, then adding organic medium yellow powder, stirring the powder to be fully wetted, putting zirconia steel balls into the powder, and grinding the powder in a grinding machine to prepare the uniformly dispersed organic medium yellow color paste;
step 2: performing surface treatment on pigment particles, performing centrifugal separation on the pigment paste, washing the pigment paste for three times by using deionized water, then dispersing the pigment paste into the deionized water, adding a polyallylammonium hydrochloride (PAH) solution into an organic pigment dispersion liquid, performing ultrasonic dispersion for 30min, performing centrifugal separation, and washing the pigment paste for three times by using the deionized water; repeating the steps to prepare pigment particles with surfaces alternately adsorbing multiple layers of PSS-PAH polyelectrolytes and positively charged;
and step 3: coating pigment particles for the first time, dispersing the pigment particles with positive electricity on the surface into an ethanol solution, adding a proper amount of water, gradually adding ammonia water under stirring to adjust the pH value of the solution to 9-10, dropwise adding a mixed solution of tetraethyl silicate (TEOS) and ethanol within 1 hour, then continuously stirring for 24 hours at room temperature, washing with water, and centrifuging for three times to obtain coated organic pigment particles for the first time;
and 4, step 4: dispersing the primary coated pigment particles in water, adding Polyallyl Ammonium Hydrochloride (PAH), ultrasonically dispersing for 30min, and then washing and centrifuging for three times; dispersing the washed and centrifuged pigment particles in water, then adding nano silica sol with the particle size of 5-20 nm, stirring and adsorbing for 60min, washing and centrifuging for three times by using water to obtain secondarily coated pigment particles, and drying to obtain the organic mesochrome with the core-shell structure.
2. Preparation of organic mesogen with core-shell structure according to claim 1The method is characterized in that: the feed ratio of organic medium yellow, PSS and water in the step 1 is mOrganic medium yellow：mPSS：mWater (W)＝0.5～1:0.5～1:100。
3. The method for preparing organic mesogen yellow with a core-shell structure according to claim 1, wherein the method comprises the following steps: in the step 2, the feed ratio of organic medium yellow, PAH, PSS and water is mOrganic medium yellow：mPAH：mPSS：mWater (W)The ratio of the PSS-PAH polyelectrolyte to the surface treatment agent is 0.5-1: 100, and the number of the adsorption layers of the surface treatment PSS-PAH polyelectrolyte is 3-6.
4. The method for preparing organic mesogen yellow with a core-shell structure according to claim 1, wherein the method comprises the following steps: the feed ratio of the organic medium yellow, the absolute ethyl alcohol, the water and the TEOS ethyl alcohol solution in the step 3 is mOrganic medium yellow：mAnhydrous ethanol：mWater (W)：mTEOS ethanol solutionThe mass concentration of the absolute ethyl alcohol solution of TEOS is 2-5 percent, wherein the ratio of TEOS to TEOS is 0.5:200: 20-30: 40.
5. The method for preparing organic mesogen yellow with a core-shell structure according to claim 1, wherein the method comprises the following steps: the feed ratio of organic medium yellow, water, PAH and nano silica sol in the step 4 is mOrganic medium yellow：mWater (W)：mPAH：mSiO2＝1:100:1:1～2。
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