阅读说明：本技术 一种颜料红57：1的制备方法 (A pigment Red 57:1 preparation method ) 是由 徐珍香 郑智剑 于 2020-07-24 设计创作，主要内容包括：一种制备C.I.颜料红57：1的工艺,通过工艺改进及加入2-氨基苯酚-4-磺酸、1-氨基-2-萘酚-4-磺酸或3-氨基-4-甲氧基苯磺酸作为第二偶合组分,减弱粒子间作用力,改变粒径和色光,同时选用十二烷基苯磺酸三乙醇胺、4-羟基丁酸肼、4-羟基丁基丙烯酸酯作为改性物质及分散剂,增强着色力,有效地控制颜料晶体成长,增大流动性,采用微波干燥,提高干燥效率,避免晶型失水转化,气流磨干燥降低颜料平均粒径,增加着色强度,本发明技术制备得到的颜料有效解决了传统颜料流动性差、着色强度低等问题。(A method of preparing c.i. pigment red 57: the process 1 comprises the steps of improving the process, adding 2-aminophenol-4-sulfonic acid, 1-amino-2-naphthol-4-sulfonic acid or 3-amino-4-methoxybenzenesulfonic acid as a second coupling component, weakening the acting force among particles, changing the particle size and the color light, simultaneously selecting dodecylbenzene sulfonic acid triethanolamine, 4-hydroxy hydrazine butyrate and 4-hydroxy butyl acrylate as modifying substances and dispersing agents, enhancing the tinting strength, effectively controlling the growth of pigment crystals, increasing the fluidity, adopting microwave drying, improving the drying efficiency, avoiding the water loss conversion of crystal forms, reducing the average particle size of the pigment by pneumatic grinding drying, and increasing the tinting strength.)

1. A process for preparing pigment Red 57: the process of 1 is characterized by comprising the following specific steps:

(1) adding 4-aminotoluene-3-sulfonic acid and 50% by mass of sodium hydroxide solution into a reaction bottle with a stirring device, cooling after 4B acid is completely dissolved, adding 36% by mass of hydrochloric acid solution at 0-10 ℃, stirring for 5-10min, adding 30% by mass of sodium nitrite aqueous solution, stirring for reaction for 35-39min, adding 40% by mass of calcium hydroxide solution, and stirring for 5-10 min;

(2) adding 2, 3-acid, 50% sodium hydroxide solution and the second coupling component into another reaction bottle with a stirring device, stirring for dissolving at 25-30 ℃, continuing to react for 20-30min, adding the modified component, and continuing to stir for 10-20 min;

(3) dropwise adding the mixed solution obtained in the step (2) into the mixed solution obtained in the step (1), adjusting the pH of the system to 8.0-9.5 by using alkali liquor, and carrying out heat preservation and stirring reaction at 70-85 ℃ for 40-60 min;

(4) and (4) filtering and rinsing the reaction liquid obtained in the step (3), drying the reaction liquid at 60-70 ℃ for 1.5-2.5h by microwave, and performing ultrafine grinding by using an airflow mill to obtain a final product.

2. Preparation of pigment red 57 according to claim 1: 1, characterized in that the molar ratio of 2, 3-acid to 4B acid in step (2) is 1: 1.03-1.05.

3. Preparation of pigment red 57 according to claim 1: 1, characterized in that in step (2) the molar ratio of 2, 3-acid to sodium hydroxide is 1: 1.3-1.5.

4. Preparation of pigment red 57 according to claim 1: the process of 1 is characterized in that the second coupling component in the step (2) is two or three of 2-aminophenol-4-sulfonic acid, 1-amino-2-naphthol-4-sulfonic acid or 3-amino-4-methoxybenzenesulfonic acid which are mixed in any proportion, and the total amount of the second coupling component is 1.5-2.5% of the total mass amount of the 2, 3-acid.

5. Preparation of pigment Red 57 according to claim 4: 1, characterized in that the second coupling component is a combination of 2-aminophenol-4-sulfonic acid and 1-amino-2-naphthol-4-sulfonic acid, the mass ratio of which is 1: 1.

6. preparation of pigment Red 57 according to claim 4: 1, characterized by the combination of 1-amino-2-naphthol-4-sulfonic acid and 3-amino-4-methoxybenzenesulfonic acid in a mass ratio of 1: 2.

7. preparation of pigment Red 57 according to claim 4: 1, characterized by the combination of 2-aminophenol-4-sulfonic acid and 3-amino-4-methoxybenzenesulfonic acid, in a mass ratio of 2: 1.

8. preparation of pigment Red 57 according to claim 4: 1, the process is characterized in that the mass ratio of the 2-aminophenol-4-sulfonic acid, the 1-amino-2-naphthol-4-sulfonic acid and the 3-amino-4-methoxybenzenesulfonic acid is 1: 1: 1.

9. preparation of pigment red 57 according to claim 1: the process of 1 is characterized in that the modification components in the step (2) are triethanolamine dodecylbenzene sulfonate, 4-hydroxy hydrazine butyrate and 4-hydroxy butyl acrylate, and the mass of the modification components is 5-7% of the theoretical yield of the pigment.

10. Preparation of pigment red 57 according to claim 1: the process of 1 is characterized in that the alkali liquor adopted in the step (3) is ammonia water or sodium carbonate aqueous solution.

Technical Field

The invention belongs to the technical field of organic raw material preparation, and particularly relates to a C.I. pigment red 57: 1. A process for producing the same.

Background

Organic pigments are an important class of colored substances used for coloring objects. Compared with inorganic pigment, the said pigment has wide variety, complete color spectrum, bright color and high coloring strength, and may be used widely in coloring ink, paint, plastic, rubber, synthetic fiber, daily chemical product, etc. and printing fabric. The c.i. pigment red 57 is the most important pigment for high quality printing red ink, and its lake salts include calcium, strontium, barium, manganese, among which calcium salt is the most widely used, and is c.i. pigment red 57:1, which accounts for about one fourth of the yield of red pigment.

C.i. pigment red 57:1 is also called lithol rubine, and the prior art is mainly to diazotize 4-aminotoluene-3-sulfonic acid (4B) at pH < 2 and temperature < 5 ℃, then couple with 2, 3-acid, use calcium ion suspension prepared by using calcium chloride as raw material as coupling lake raw material and adjust pH alkaline condition, and prepare pigment red 57 by coupling salting out: 1. however, the pigment prepared by the method has the defects of low dispersibility, low coloring strength and the like. With the pigment red 57 in domestic and foreign markets: 1, and the quality is required to be improved, and therefore, improvement of pigment red 57:1, improving the product quality.

Disclosure of Invention

The invention aims to overcome the defects of the prior pigment red 57:1, the production process and the product quality are insufficient, and the preparation of the pigment red 57:1, by adding coupling components and modified additives and the like, the interaction force among particles and the surface polarity state of pigment particles are adjusted, the particle size is improved, and the performances of the product such as flowability, dispersibility, tinting strength and the like are improved.

In order to achieve the purpose, the invention adopts the following technical scheme:

a process for preparing pigment Red 57:1, the specific steps are as follows:

(1) adding 4-aminotoluene-3-sulfonic acid and 50% by mass of sodium hydroxide solution into a reaction bottle with a stirring device, cooling after 4B acid is completely dissolved, adding 36% by mass of hydrochloric acid solution at 0-10 ℃, stirring for 5-10min, adding 30% by mass of sodium nitrite aqueous solution, stirring for reaction for 35-39min, adding 40% by mass of calcium hydroxide solution, and stirring for 5-10 min;

(2) adding 2, 3-acid, 50% sodium hydroxide solution and the second coupling component into another reaction bottle with a stirring device, stirring for dissolving at 25-30 ℃, continuing to react for 20-30min, adding the modified component, and continuing to stir for 10-20 min;

(3) dropwise adding the mixed solution obtained in the step (2) into the mixed solution obtained in the step (1), adjusting the pH of the system to 8.0-9.5 by using alkali liquor, and carrying out heat preservation and stirring reaction at 70-85 ℃ for 40-60 min;

the step is mainly coupling and color precipitation, and the coupling component (2) is added into the diazonium salt (1) for trans-coupling, so that the fluidity and the transparency are better.

(4) Filtering and rinsing the reaction liquid obtained in the step (3), drying the reaction liquid for 1.5 to 2.5 hours at the temperature of between 60 and 70 ℃, and carrying out ultrafine grinding by adopting an airflow mill.

In the step (1), the molar ratio of the 4B acid to the sodium hydroxide to the hydrochloric acid is 1: 1.5-2.0: 2.8-3.5.

In the step (1), the molar ratio of the 4B acid to the sodium nitrite is 1: 1.03-1.06.

In the step (1), the molar ratio of the 4B acid to the calcium hydroxide is 1: 1.05-1.12.

In the step (2), the molar ratio of the 2, 3-acid to the 4B acid is 1: 1.03-1.05.

In the step (2), the molar ratio of the 2, 3-acid to the sodium hydroxide is 1: 1.3-1.5. The sodium hydroxide is mainly used for adjusting the coupling pH, because the pigment shows different characteristics under different pH values, for example, the pigment is brighter in color and has high fluidity and more stable crystal form when the pH value is 8.0-9.5, but when the pH value is increased again, the transparency is good, but the fluidity is lower.

The second coupling component in the step (2) is two or three of 2-aminophenol-4-sulfonic acid, 1-amino-2-naphthol-4-sulfonic acid or 3-amino-4-methoxybenzenesulfonic acid which are mixed in any proportion. The total dosage of the compound is 1.5 to 2.5 percent of the total mass dosage of the 2, 3-acid.

Preferably, the second coupling component is a combination of 2-aminophenol-4-sulfonic acid and 1-amino-2-naphthol-4-sulfonic acid in a mass ratio of 1: 1;

preferably, the mass ratio of the 1-amino-2-naphthol-4-sulfonic acid to the 3-amino-4-methoxybenzenesulfonic acid is 1: 2;

preferably, the mass ratio of the 2-aminophenol-4-sulfonic acid to the 3-amino-4-methoxybenzenesulfonic acid is 2: 1;

preferably, the mass ratio of the 2-aminophenol-4-sulfonic acid to the 1-amino-2-naphthol-4-sulfonic acid to the 3-amino-4-methoxybenzenesulfonic acid is 1: 1: 1.

the modified components in the step (2) are dodecyl benzene sulfonic acid triethanolamine, 4-hydroxy butyric acid hydrazine and 4-hydroxy butyl acrylate, and the mass of the modified components is 5-7% of the theoretical yield of the pigment.

The alkali liquor adopted in the step (3) is ammonia water or sodium carbonate aqueous solution.

The pigment red described herein is c.i. pigment red.

The invention has the beneficial effects that:

aiming at the problems of poor fluidity, low coloring strength and the like of the pigment prepared by the prior art, the invention adds 2-aminophenol-4-sulfonic acid, 1-amino-2-naphthol-4-sulfonic acid or 3-amino-4-methoxybenzenesulfonic acid as a second coupling component, the selected second coupling component contains an electron-withdrawing group sulfonic group, the induction and conjugation effects of the second coupling component can effectively reduce the electron cloud density, and electron-donating groups such as hydroxyl, amino and the like can increase the electron cloud density of a conjugation system, so that the maximum absorption wavelength is in red shift. The co-coupling process of the second coupling component weakens the acting force among particles, changes the particle size and the color light and improves the transparency.

On the other hand, the triethanolamine dodecylbenzene sulfonate is selected as a modifying substance and can also play a role of a dispersing agent, one end of the triethanolamine dodecylbenzene sulfonate has long chain hydrocarbon, ester group or double bond with hydrophobicity and is used as a lipophilic group, the wetting angle is very large, the tinting strength is strong, the other end of the triethanolamine dodecylbenzene sulfonate contains hydrophilic groups such as sulfonic group and hydroxyl group, and the hydrophilic groups can be well adsorbed or covered on the surface of particles.

Adopt microwave drying, the object of being heated itself is the heat-generating body, does not need hot conductive process, and the heat penetrates inside and outside the object from all sides and makes the object reach even heating in the very short time simultaneously, and non-traditional by outside and in dry, has shortened drying time greatly, accomplishes even heating and even drying simultaneously. Use microwave drying, can avoid using high temperature can reach fine drying effect, avoided pigment red 57 in the high temperature drying: the alpha and gamma crystal forms in 1 are dehydrated and transformed into beta and crystal forms respectively, thereby causing the change of chromatic light.

The average particle size of the pigment is reduced to increase the coloring strength, namely, the coloring power depends on the dispersion level of the pigment to a great extent, the pigment is crushed by an air flow mill, the collision frequency between particles is far higher than that between the particles and the wall of the container, the pigment can achieve a better crushing effect, the surface morphology of the pigment is damaged while the particle size of the pigment is reduced, active sites are increased, the activity of pigment seed crystals is improved, meanwhile, the agglomeration of the pigment can be avoided by the air flow mill grinding, the agglomeration degree of the pigment seed crystals is reduced, and the pigment has better dispersity and coloring degree.

Detailed Description

The present invention will be further illustrated by the following examples, which are intended to be merely illustrative and not limitative.