CI Pigment Red 224 mixed crystal and prefabricated solid, preparation method and use

Abstract

A CI Pigment Red 224 mixed crystal and preformed solid, a preparation method and use thereof, relating to the field of coloring pigments; the preparation method comprises the following steps: step (1): adding the pigment mixed crystal to dilute sulfuric acid, heating to 40-90°C under stirring, and continuously dripping hydrogen peroxide; step (2): continuing to heat to a reaction temperature not higher than 100°C, and stopping heating after the reaction ends; step (3): filtering after cooling, washing the product with water, filtering, and drying to obtain a CI Pigment Red 224 mixed crystal preformed solid; the CI Pigment Red 224 mixed crystal preformed solid of the scheme has a color light similar to that of CI Pigment Red 224 after pigmentation, can completely replace the traditional preparation process of CI Pigment Red 224, and solves the problems of high energy consumption, high material consumption and high pollution in the existing preparation process of CI Pigment Red 224.

Description

Technical Field

[0001] The invention relates to the field of coloring pigments, and in particular to a CI Pigment Red 224 mixed crystal and a prefabricated solid, a preparation method and an application thereof. Background Art

[0002] Perylene pigments are a class of high-performance pigments. Their chemical stability, thermal stability and application performance are incomparable to those of ordinary pigments. CI Pigment Red 224 (chemical name: 3,4,9,10-perylenetetracarboxylic dianhydride, compound 1) is a unique red variety among perylene pigments, mainly used for the preparation of automotive coatings. This is mainly because the pigment is a key intermediate in the preparation of perylene pigments. In other words, except for CI Pigment Violet 29 (chemical name: perylene imide, compound 3), all perylene pigments are its imide derivatives.

[0003] The conventional preparation method of compound 1 is as follows: 1,8-naphthalene imide (compound 2) is subjected to an alkali fusion reaction in molten KOH at 220-250°C to form perylene imide (compound 3), which is then converted into compound 1 by an oxidation reaction in 98% sulfuric acid at 150-200°C. The chemical reaction formula is as follows:

[0004] ;

[0005] The above-mentioned method for manufacturing compound 1 has the defect that the alkali fusion reaction of solid 1,8-naphthalimide in molten KOH to generate perylene imide needs to be carried out at 220-250°C, because the reaction is carried out in a KOH melt and the viscosity of the reactants is very high. In order to make the reactants have good fluidity, the amount of KOH used is more than 3 times the weight of 1,8-naphthalimide. Despite this, the mass transfer between the reactants is still not sufficient, resulting in a relatively complex composition of the alkali fusion reaction product. After the reaction is completed, in order to obtain the desired product, it is necessary to dilute with water so that perylene imide is precipitated from the dilute alkali solution, thus consuming a large amount of KOH. After liquid / solid separation, the solid is perylene imide with a purity of about 50%, and the liquid is a waste alkali solution with almost no utilization value. In order to treat this dilute alkali solution, a large amount of acid must be used to neutralize it, thereby producing a large amount of salt with no recovery value. Since the alkali fusion reaction is carried out at 220-250°C, side reactions will inevitably occur during the reaction process, so the yield of synthesizing perylene imide using traditional alkali fusion reaction conditions is less than 50%. After the obtained perylene imide is oxidized and converted into compound 1 at 200°C in 98% sulfuric acid, its purity cannot meet the requirements of subsequent pigment production. It needs to be refined by "alkali dissolution-acid precipitation" (the crude product with low purity is first dissolved in KOH solution, hot filtered, and then sulfuric acid is added to adjust the filtrate to acidity to precipitate the product with higher purity). In this stage, a large amount of sulfuric acid and KOH are consumed. According to incomplete statistical data, using the above traditional process, 2.5-3 tons of compound 21, 6-7 tons of KOH and 20 tons of 98% sulfuric acid are required to produce 1 ton of compound 1 with a purity of about 98%. Therefore, the above traditional method for preparing compound 1 has the defects of lengthy reaction steps, large consumption of chemicals and environmental unfriendliness, and is a high energy consumption, high material consumption and high pollution manufacturing process. Summary of the invention

[0006] The purpose of the present invention is to provide a method for preparing a CI Pigment Red 224 mixed crystal preformed solid, which can prepare a CI Pigment Red 224 mixed crystal preformed solid with low energy consumption, low material consumption and low pollution. The color light of the CI Pigment Red 224 mixed crystal preformed solid after pigmentation is close to that of CI Pigment Red 224, and can completely replace the traditional preparation process of CI Pigment Red 224.

[0007] The present invention also provides a method for preparing CI Pigment Red 224 mixed crystal, which comprises subjecting a prefabricated solid to a pigmentation process.

[0008] The present invention also provides a CI Pigment Red 224 mixed crystal preformed solid, which is prepared using the above-mentioned preparation method.

[0009] The present invention also provides a CI Pigment Red 224 mixed crystal, which is prepared by the above-mentioned mixed crystal preparation method.

[0010] The invention also provides a use of a prefabricated solid in preparing a pigment with a color similar to that of CI Pigment Red 224.

[0011] To achieve this object, the present invention adopts the following technical solutions:

[0012] A method for preparing a CI Pigment Red 224 mixed crystal preformed solid comprises the following steps:

[0013] Step (1): adding the pigment mixed crystals to dilute sulfuric acid with a concentration of 40-70%, heating to 40-90°C under stirring, and continuously adding hydrogen peroxide;

[0014] Pigment mixed crystals include:

[0015] , and ;

[0016] Step (2): Continue to raise the temperature to a reaction temperature not higher than 100° C., and stop heating after the reaction ends;

[0017] Step (3): cooling and filtering, washing the product with water and filtering it, and drying it to obtain a CI Pigment Red 224 mixed crystal preformed solid;

[0018] CI Pigment Red 224 mixed crystal preformed solid includes:

[0019] , and .

[0020] It can be optimized that step (S) is also performed before step (1);

[0021] The step (S) comprises:

[0022] Step (S1): under the protection of an inert gas, adding reaction raw material 1 and reaction raw material 2 into a reaction mixed solvent at a molar ratio of 1: (0.01-0.10);

[0023] Reaction material 1 is ;

[0024] Reaction material 2 is ;

[0025] Step (S2): heating to 150-200°C for reaction, and stopping heating after the reaction is completed;

[0026] Step (S3): naturally cooling to room temperature, filtering after dilution, washing, and drying to obtain a dark red solid; the dark red solid is used as the pigment mixed crystal in step (1).

[0027] Preferably, in the step (S1), the reaction mixed solvent comprises: an organic base and an organic solvent;

[0028] Organic solvents include: o-dichlorobenzene and / or 1,2,4-trichlorobenzene;

[0029] The organic base includes at least one of 1,8-diazabicycloundec-7-ene, 2-(di-n-butyl)ethanolamine and 1,5-dioxabicyclo[4.3.0]non-5-ene.

[0030] Preferably, in the step (S1), the preparation method of the reaction raw material 2 includes:

[0031] Step (S1-1): under the protection of inert gas, anhydrous ethanol is added to a reaction container, 1,8-naphthalene anhydride and 3,5-xylidine are added under stirring, the temperature is raised to reflux, and the reaction is carried out for a period of time;

[0032] Step (S1-2): tracking the reaction by silica gel thin plate chromatography (TLC), and stopping heating after the reaction is completed;

[0033] Step (S1-3): naturally cool to room temperature and filter, wash the filter cake, and dry to obtain a pink reaction raw material 2.

[0034] Optimally, step (S4) is performed after step (S3);

[0035] Step (S4): The filtered mother liquor after filtering in step (S3) and the washing liquid after washing are subjected to reduced pressure distillation to recover the monohydric fatty alcohol and the reaction mixed solvent respectively.

[0036] A method for preparing a CI Pigment Red 224 mixed crystal comprises the method for preparing a CI Pigment Red 224 mixed crystal preformed solid as described above, wherein the CI Pigment Red 224 mixed crystal preformed solid obtained in step (3) is subjected to pigmentation processing.

[0037] Optimally pigmented processing:

[0038] The CI Pigment Red 224 mixed crystal preformed solid prepared in step (3) is added with an inorganic salt, an organic salt and a ball milling solvent, and transferred to a ball mill for ball milling, sieved to screen out steel balls, poured into hot water, stirred and filtered, the filter cake is washed with water until the conductivity of the filtrate is less than 300 microsiemens, and dried to obtain CI Pigment Red 224 mixed crystal;

[0039] The mass ratios of CI Pigment Red 224 mixed crystal preformed solid, steel balls, inorganic salt, ball milling solvent and organic salt are: (1-30): (50-150): (15-25): (2-6): 1.

[0040] A CI Pigment Red 224 mixed crystal preformed solid is prepared by the above-mentioned method for preparing a CI Pigment Red 224 mixed crystal preformed solid.

[0041] A CI Pigment Red 224 mixed crystal is prepared by the above-mentioned method for preparing a CI Pigment Red 224 mixed crystal.

[0042] A use of a preformed solid in preparing a pigment with a color similar to that of CI Pigment Red 224, wherein the preformed solid is prepared by the above-mentioned method for preparing a CI Pigment Red 224 mixed crystal preformed solid.

[0043] Compared with the prior art, one of the above technical solutions has the following beneficial effects:

[0044] The present invention provides a method for preparing a CI Pigment Red 224 mixed crystal preformed solid, which can prepare a CI Pigment Red 224 mixed crystal preformed solid with low energy consumption, low material consumption and low pollution. The color light of the CI Pigment Red 224 mixed crystal preformed solid after pigmentation is close to that of CI Pigment Red 224, and the mixed crystal preformed solid can completely replace the traditional preparation process of CI Pigment Red 224, thereby solving the problems of high energy consumption, high material consumption and high pollution in the existing preparation process of CI Pigment Red 224. DETAILED DESCRIPTION

[0045] For ease of understanding of the present invention, the present invention is described more fully below. The present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present invention more thorough and comprehensive. If no specific technology or conditions are indicated in the embodiments, the technology or conditions described in the documents in this area or the product instructions are carried out. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products that can be obtained by commercial purchase.

[0046] A method for preparing a CI Pigment Red 224 mixed crystal preformed solid comprises the following steps:

[0047] Step (1): adding the pigment mixed crystals to dilute sulfuric acid with a concentration of 40-70%, heating to 40-90°C under stirring, and continuously adding hydrogen peroxide;

[0048] Pigment mixed crystals include:

[0049] , and ;

[0050] Compared with the prior art, the perylene imide obtained by the reaction is directly oxidized in 98% sulfuric acid with hydrogen peroxide as an oxidant to obtain CI Pigment Red 224; this scheme only needs to use dilute sulfuric acid, and does not need to use concentrated sulfuric acid. The specific concentration of dilute sulfuric acid is defined as a concentration below 70% according to common sense. When the concentration is below 70%, the oxidizing property decreases, and the oxidizing property in the reactant is mainly provided by hydrogen peroxide; this scheme uses hydrogen peroxide for oxidation, which can avoid and Direct oxidation can make the color of the final CI Pigment Red 224 mixed crystal preformed solid close to CI Pigment Red 224 after pigmentation.

[0051] The concentrations of dilute sulfuric acid and hydrogen peroxide can be determined as needed. In the best embodiment of this scheme, the concentration is controlled at 40-60%, and the concentration of hydrogen peroxide is controlled at 20-40%. At the same time, a catalyst accounting for less than 5% of the total mass can also be added as needed. The catalyst is the one used in the well-known CI Pigment Red 224, such as AlCl3 as a catalyst.

[0052] Step (2): Continue to raise the temperature to a reaction temperature not higher than 100° C., and stop heating after the reaction ends;

[0053] The reaction temperature can be determined as required, as long as it is not higher than 100°C, for example, any temperature between 60-100°C; therefore, the reaction temperature is mild, the reaction controllability is high, the degree of side reactions is extremely low, and thus the yield of the final product is high.

[0054] Step (3): cooling and filtering, washing the product with water and filtering it, and drying it to obtain a CI Pigment Red 224 mixed crystal preformed solid;

[0055] CI Pigment Red 224 mixed crystal preformed solid includes:

[0056] , and .

[0057] CI Pigment Red 224 mixed crystal preformed solid contains three main components. The color light of the three components is very close to CI Pigment Red 224. It can replace CI Pigment Red 224 and overcome the high energy consumption, high material consumption and high pollution problems faced in the traditional preparation of CI Pigment Red 224. Especially for dispersion and dyeing, CI Pigment Red 224 in the original process is very easy to aggregate into hard particles due to the good flatness of the product structure, and is not easy to disperse plastic and paint dyeing. It is also a planar structure, which is equivalent to using the planar structure to stack the molecules like layers; and for dispersion, this scheme also generates two other isomers and , adding two adjacent planar structures, thereby increasing the gap between molecules, making the material easier to disperse and easier to dye.

[0058] The present invention provides a method for preparing a CI Pigment Red 224 mixed crystal preformed solid, which can prepare a CI Pigment Red 224 mixed crystal preformed solid with low energy consumption, low material consumption and low pollution. The color light of the CI Pigment Red 224 mixed crystal preformed solid after pigmentation is close to that of CI Pigment Red 224, and the mixed crystal preformed solid can completely replace the traditional preparation process of CI Pigment Red 224, thereby solving the problems of high energy consumption, high material consumption and high pollution in the existing preparation process of CI Pigment Red 224.

[0059] The raw materials of the pigment mixed crystal of this scheme can be directly purchased from the market separately and then prepared by mixing the ingredients. Or it can be prepared by using the raw materials in the traditional CI Pigment Red 224 preparation process; specifically, step (S) is also performed before step (1);

[0060] The step (S) comprises:

[0061] Step (S1): under the protection of an inert gas, adding reaction raw material 1 and reaction raw material 2 into a reaction mixed solvent at a molar ratio of 1: (0.01-0.10);

[0062] Reaction material 1 is ;

[0063] Reaction material 2 is ;

[0064] Step (S2): heating to 150-200°C for reaction, and stopping heating after the reaction is completed;

[0065] Step (S3): naturally cooling to room temperature, filtering after dilution, washing, and drying to obtain a dark red solid; the dark red solid is used as the pigment mixed crystal in step (1).

[0066] Step (S) can be performed before step (1). Reaction raw materials 1 and 2 can be subjected to ring fusion reaction at 150-200°C to directly obtain a dark red solid, which can be directly used as a reaction raw material for pigment mixed crystals. The chemical reaction formula of step (S2) is:

[0067] ;

[0068] The dark red solid is then used as the pigment mixed crystal in step (1) and step (2) is continued. The chemical reaction formula of step (2) is:

[0069] .

[0070] In this way, step (S) and step (1) can be seamlessly connected and executed, and there is no need to purchase the raw materials of the pigment mixed crystal on the market. The optimal molar ratio of reaction raw material 1 to reaction raw material 2 is 1: (0.01-0.10) to make the dark red solid color closest to CI Pigment Red 224. In terms of mass percentage, 90-97% of CI Pigment Red 224 can be directly obtained from the pigment mixed crystal. 2-7% and the remainder Of course, the above three pigment mixed crystal raw materials can be directly purchased on the market and directly synthesized according to the above ratio.

[0071] Preferably, in the step (S1), the reaction mixed solvent comprises: an organic base and an organic solvent;

[0072] Organic solvents include: o-dichlorobenzene and / or 1,2,4-trichlorobenzene;

[0073] The organic base includes at least one of 1,8-diazabicycloundec-7-ene, 2-(di-n-butyl)ethanolamine and 1,5-dioxabicyclo[4.3.0]non-5-ene.

[0074] The organic base and the organic solvent are used to provide dissolution for the reaction raw materials 1 and 2. The organic solvent includes: o-dichlorobenzene and / or 1,2,4-trichlorobenzene; the organic base includes: at least one of 1,8-diazabicycloundec-7-ene (DBU), 2-(di-n-butyl)ethanolamine (DAA) and 1,5-dioxabicyclo[4.3.0]non-5-ene (DBN). On the one hand, the reaction mixed solvent provides the best dissolution effect for the reaction raw materials 1 and 2, and on the other hand, the solvent recovery degree of the reaction mixed solvent is the best, and the CI Pigment Red 224 mixed crystal preformed solid can be prepared with lower energy consumption, lower material consumption and lower pollution.

[0075] Preferably, in the step (S1), the preparation method of the reaction raw material 2 includes:

[0076] Step (S1-1): under the protection of inert gas, anhydrous ethanol is added to a reaction container, 1,8-naphthalene anhydride and 3,5-xylidine are added under stirring, the temperature is raised to reflux, and the reaction is carried out for a period of time;

[0077] Step (S1-2): tracking the reaction by silica gel thin plate chromatography (TLC), and stopping heating after the reaction is completed;

[0078] Step (S1-3): naturally cool to room temperature and filter, wash the filter cake, and dry to obtain a pink reaction raw material 2.

[0079] The reaction raw material 2 of this scheme can be directly purchased from the market or synthesized by oneself; the synthetic raw materials are 1,8-naphthoic anhydride and 3,5-xylidine, which can reduce the use cost of the reaction raw material 2, and the yield of the reaction raw material 2 prepared by this method can reach 95%. The molar ratio of 1,8-naphthoic anhydride to 3,5-xylidine can be close to 1:1, but in order to achieve a more complete reaction effect, 3,5-xylidine can be made excessive relative to 1,8-naphthoic anhydride, that is, the actual molar ratio can be 1:(1.01-1.3).

[0080] The reaction formula is as follows:

[0081] ;

[0082] The solvent used in at least one step of dilution, filtration and washing is a monohydric fatty alcohol, and the carbon number of the monohydric fatty alcohol is less than 6.

[0083] The carbon number of the monohydric fatty alcohol is less than 6, for example, it is selected from one or more combinations of methanol, ethanol and isopropanol. In the best embodiment, only methanol is needed for dilution, filtering and washing respectively; the simpler the composition of the monohydric fatty alcohol, the easier it is to recycle, the lower the material consumption and the lower the pollution, especially the low cost of using methanol and ethanol.

[0084] Optimally, step (S4) is performed after step (S3);

[0085] Step (S4): The filtered mother liquor after filtering in step (S3) and the washing liquid after washing are subjected to reduced pressure distillation to recover the monohydric fatty alcohol and the reaction mixed solvent respectively.

[0086] Step (S4) can be used to recover monohydric fatty alcohol and reaction mixed solvent. The filtered mother liquor and the washing liquid after washing can be directly recovered by vacuum distillation. The main solvent in the mixed crystal preparation process of CI Pigment Red 224 can be recycled and reused, avoiding the generation of waste alkali liquid and the problem of a large amount of acid neutralization waste liquid. The problems of high energy consumption, high material consumption and high pollution faced in the traditional preparation of CI Pigment Red 224 can be overcome.

[0087] A method for preparing a CI Pigment Red 224 mixed crystal comprises the method for preparing a CI Pigment Red 224 mixed crystal preformed solid according to any of the above embodiments, wherein the CI Pigment Red 224 mixed crystal preformed solid obtained in step (3) is subjected to a pigmentation processing.

[0088] After the CI Pigment Red 224 mixed crystal preformed solid is prepared, it can be processed through the known pigment processing procedures, mainly through a series of chemical, physical and mechanical treatments and other appropriate process methods to change the crystal form, size, aggregation state and surface state of the particles, so that it has the required application performance. Common solvent treatment method, salt grinding method, surface treatment method, etc., the specific process can be determined according to actual needs.

[0089] Optimally pigmented processing:

[0090] The CI Pigment Red 224 mixed crystal preformed solid prepared in step (3) is added with an inorganic salt, an organic salt and a ball milling solvent, and transferred to a ball mill for ball milling, sieved to screen out steel balls, poured into hot water, stirred and filtered, the filter cake is washed with water until the conductivity of the filtrate is less than 300 microsiemens, and dried to obtain CI Pigment Red 224 mixed crystal;

[0091] The mass ratios of CI Pigment Red 224 mixed crystal preformed solid, steel balls, inorganic salt, ball milling solvent and organic salt are: (1-30): (50-150): (15-25): (2-6): 1.

[0092] The inorganic salt can be determined according to the raw materials required by the existing salt milling method; in the best embodiment, the inorganic salt can be anhydrous calcium chloride; the ball milling solvent can be butyl acetate; and the organic salt can be calcium stearate.

[0093] A CI Pigment Red 224 mixed crystal preformed solid is prepared by the preparation method of a CI Pigment Red 224 mixed crystal preformed solid according to any of the above embodiments.

[0094] A CI Pigment Red 224 mixed crystal is prepared by the preparation method of a CI Pigment Red 224 mixed crystal of any of the above embodiments.

[0095] A use of a preformed solid in preparing a pigment with a color similar to that of CI Pigment Red 224, wherein the preformed solid is prepared by the preparation method of a CI Pigment Red 224 mixed crystal preformed solid according to any of the above embodiments.

[0096] The reaction raw material 2 used in the specific embodiment of this scheme is mainly synthesized by itself, and the specific preparation method is as follows:

[0097] Under nitrogen protection, anhydrous ethanol (250 ml) was added to a 500 mL three-necked flask, and 1,8-naphthalene anhydride (39.6 g, 0.20 mol) and 3,5-xylidine (26.5 g, 0.21 mol) were added under stirring. After the addition was completed, the temperature was raised to reflux and the reaction was carried out for 3 h. The reaction was tracked by silica gel thin plate chromatography (TLC). After the reaction was completed, the heating was stopped, the mixture was naturally cooled to room temperature, filtered, and the filter cake was washed with ethanol and water successively. After drying, a pink reaction raw material 2 (57.2 g) was obtained with a yield of 95%.

[0098] Embodiment 1:

[0099] Preparation of pigment mixed crystals:

[0100] Under nitrogen protection, 2-(di-n-butyl)ethanolamine (DAA) (51.9 g, 0.30 mol), 1,8-diazabicycloundec-7-ene (DBU) (76.0 g, 0.50 mol) and o-dichlorobenzene (180 g) were added to a 500 mL three-necked flask, and reaction raw material 1 (39.4 g, 0.2 mol) and reaction raw material 2 (2.4 g, 8 mg) were added under stirring. After the addition was completed, the temperature was raised to 170°C and tracked by silica gel thin plate chromatography (TLC). When the spots of reaction raw material 1 basically disappeared (about 10 h), the heating was stopped, and the mixture was naturally cooled to room temperature. After dilution with methanol, it was filtered, and the filter cake was washed with methanol until there was no o-dichlorobenzene smell to obtain a washing liquid. After the filter cake was dried, a dark red solid (36 g) was obtained, which was the pigment mixed crystal. The filtered mother liquor and the washing liquid are subjected to reduced pressure distillation respectively to recover methanol, 1,8-diazabicycloundec-7-ene (DBU), 2-(di-n-butyl)ethanolamine (DAA) and o-dichlorobenzene respectively.

[0101] Preparation of CI Pigment Red 224 mixed crystal preformed solid:

[0102] Add 50% sulfuric acid (400g) and pigment mixed crystal (dark red solid, 36g) into a 1L enamel cup. Heat the reactants to 60℃ while stirring. Add 30% hydrogen peroxide (250g) dropwise within 6h. Add 1g of AlCl3 as a catalyst. After the addition is complete, raise the temperature to 100℃ for reaction. After 6h, take samples every 2h to detect the reaction end point. After the reaction is completed, stop heating, cool naturally to 50℃, filter, wash the filter cake with hot water until it is neutral, and dry to obtain a bright red solid (36g).

[0103] Embodiment 2:

[0104] Preparation of pigment mixed crystals:

[0105] Under nitrogen protection, 2-(di-n-butyl)ethanolamine (DAA) (69.3 g, 0.40 mol), 1,8-diazabicycloundec-7-ene (DBU) (83.6 g, 0.55 mol) and 1,2,4-trichlorobenzene (200 g) were added to a 500 mL three-necked flask, and reaction raw material 1 (39.4 g, 0.20 mol) and reaction raw material 2 (2.4 g, 8 mg) were added under stirring. After the addition was completed, the temperature was raised to 180 ° C for reaction, and TLC tracking (about 9 h) was performed. The heating was stopped, and the mixture was naturally cooled to room temperature. After dilution with ethanol, it was filtered, and the filter cake was washed with ethanol until there was no 1,2,4-trichlorobenzene odor. After the filter cake was dried, a dark red solid (34 g) was obtained, which was the pigment mixed crystal. The filtered mother liquor and the washing liquid are subjected to reduced pressure distillation to recover methanol, 1,8-diazabicycloundec-7-ene (DBU), 2-(di-n-butyl)ethanolamine (DAA) and 1,2,4-trichlorobenzene respectively.

[0106] The preparation steps of CI Pigment Red 224 mixed crystal preformed solid are the same as those in Example 1.

[0107] Embodiment 3:

[0108] Preparation of pigment mixed crystals:

[0109] Under nitrogen protection, 2-(di-n-butyl)ethanolamine (DAA) (69.3 g, 0.40 mol), 1,5,7-triazabicyclo[4.4.0]dec-5-ene (DBN) (76.5 g, 0.55 mol) and o-dichlorobenzene (180 g) were added to a 500 mL three-necked flask, and reaction raw material 1 (39.4 g, 0.20 mol) and reaction raw material 2 (2.4 g, 8 mg) were added under stirring. After the addition was completed, the temperature was raised to 170 ° C for reaction, and TLC tracking was performed (about 10 h). The heating was stopped, and the mixture was naturally cooled to room temperature. After dilution with ethanol, it was filtered, and the filter cake was washed with ethanol until there was no o-dichlorobenzene odor. After drying, a dark red solid (35.5 g) was obtained, which was the pigment mixed crystal. The filtered mother liquor and the washing liquid are subjected to reduced pressure distillation respectively to recover ethanol, 2-(di-n-butyl)ethanolamine (DAA), 1,5,7-triazabicyclo[4.4.0]dec-5-ene (DBN) and o-dichlorobenzene respectively.

[0110] The preparation steps of CI Pigment Red 224 mixed crystal preformed solid are the same as those in Example 1.

[0111] Embodiment 4:

[0112] Under nitrogen protection, 2-(di-n-butyl)ethanolamine (DAA) (51.9 g, 0.30 mol), 1,8-diazabicycloundec-7-ene (DBU) (83.6 g, 0.55 mol) and 1,2,4-trichlorobenzene (180 g) were added to a 500 mL three-necked flask, and reaction raw material 1 (39.4 g, 0.20 mol) and reaction raw material 2 (2.4 g, 8 mg) were added under stirring. After the addition was completed, the temperature was raised to 180 ° C for reaction, and TLC tracking was performed (about 9 h). The heating was stopped, and the mixture was naturally cooled to room temperature. After dilution with ethanol, it was filtered, and the filter cake was washed with ethanol until there was no o-dichlorobenzene odor. After drying, a dark red solid (36 g) was obtained, which was the pigment mixed crystal. The filtered mother liquor and the washing liquid are subjected to reduced pressure distillation respectively to recover ethanol, 2-(di-n-butyl)ethanolamine (DAA), 1,8-diazabicycloundec-7-ene (DBU) and 1,2,4-trichlorobenzene respectively.

[0113] The preparation steps of CI Pigment Red 224 mixed crystal preformed solid are the same as those in Example 1.

[0114] The CI Pigment Red 224 mixed crystal preformed solids obtained in Examples 1-4 were respectively processed into pigments by ball milling. The ingredients for ball milling are shown in Table 1, and the ball milling was carried out in a planetary ball mill. After the ball milling, the ball milled material was poured into 20 times the weight of hot water, stirred for 1 hour, and then filtered. The filter cake was washed with hot water and deionized water until the conductivity of the filtrate was less than 300 microsiemens, and dried at 60° C. to constant weight, respectively, to obtain CI Pigment Red 224 mixed crystals of Examples 1-4.

[0115] Table 1-Ball milling ingredients

[0116]

[0117] Comparative Example:

[0118] The commercial Perylene Brilliant Red S-0499 was used as a standard sample. The Perylene Brilliant Red S-0499 was prepared by a traditional process and its performance was measured in comparison with Examples 1 to 4 of the present application.

[0119] To this end, Examples 1-4 and the comparative example were prepared into pigment pastes, specifically using the following known process:

[0120] In a covered glass bottle, glass beads (2.5 mm in diameter, 60 g), 7.5 g of the sample to be tested (CI Pigment Red 224 mixed crystals of Examples 1-4 and the comparative example), 7.5 g of a dispersant (a mixture of dispersant 24000 purchased from Lubrizol Specialty Chemicals (Shanghai) Co., Ltd., USA) and butyl acetate in a mass ratio of 1:1), 20 g of a diluent (a mixture of butyl acetate and ethanol in a mass ratio of 1:1) were added, the cover was put on, and it was sealed with tape. The glass bottle was placed on a pigment oscillator (purchased from Wanjiang Weihong Instrument Business Department, Dongguan City), and the pigment fineness was oscillated to be less than 15 μ (detected by a Hegman particle size analyzer), and then 35 g of a diluent (a mixture of butyl acetate and ethanol in a mass ratio of 1:1) was added to obtain the pigment paste corresponding to Examples 1-4 and the comparative example.

[0121] The pigment color and tinting power were measured for Examples 1-4 and Comparative Examples:

[0122] Preparation of color card for measuring pigment color: Use a pipette to take 4-5 ml of the pigment paste prepared in step (1), drop it on the color card paper, and use a 3K scraper to scrape the sample to obtain a color card for measuring the pigment color.

[0123] Preparation of color card for determining pigment tinting power: Take 5g of the prepared pigment paste, add it to 10g of water-based white paint (white latex paint B1, Shanghai Nippon Paint Co., Ltd.), stir it evenly with a high-speed stirrer to obtain a pigment-white paste. Use a pipette to draw 4-5ml of the pigment-white paste, drop it on the color card paper, and scrape it with a 3K scraper to obtain a color card for testing the pigment tinting power. The pigment tinting power is expressed by the K / S value. After the color paste on the above color card is dry, the color card is tested for the pigment color and pigment tinting power on a colorimeter (purchased from Datacolor, USA). The specific results are shown in Tables 2 and 3.

[0124] In Table 2 and Table 3, L is brightness. If the difference between the L value of the sample under test and the standard sample is positive, it means that the sample under test is brighter than the standard sample. On the contrary, if the difference between the L value of the sample under test and the standard sample is negative, it means that the sample under test is darker than the standard sample. The larger the absolute value of the difference, the greater the degree of deviation.

[0125] a is the red-green degree. If the difference between the a value of the sample under test and the standard sample is positive, it means that the sample under test is redder than the standard sample. On the contrary, if the difference between the a value of the sample under test and the standard sample is negative, it means that the sample under test is greener than the standard sample. The larger the absolute value of the difference, the greater the degree of deviation.

[0126] b is the yellow-blue degree. If the b value difference between the sample under test and the standard sample is positive, it means that the sample under test is yellower than the standard sample. On the contrary, if the b value difference between the sample under test and the standard sample is negative, it means that the sample under test is bluer than the standard sample. The larger the absolute value of the difference, the greater the degree of deviation.

[0127] ΔE* is a comprehensive color difference indicator. The larger the value, the greater the degree of total color difference. Usually, the qualified value of ΔE* of the sample is between 1% and 2%.

[0128] The K / S value is the depth of the color, and the larger the value, the higher the tinting strength.

[0129] Table 2- Pigment color test data

[0130]

[0131] Table 3- Pigment tinting strength test data

[0132]

[0133] illustrate:

[0134] The comparative example is Perylene Brilliant Red S-0499, which is a conventional CI Pigment Red 224 color development; and according to Table 2, the values ​​of brightness, redness, greenness, and yellowness and blueness of Examples 1 to 4 are basically close to those of Perylene Brilliant Red S-0499, and the qualified value of ΔE* is between 1% and 2%, which shows that the CI Pigment Red 224 mixed crystal of the present application is close to the color light of Perylene Brilliant Red S-0499, and can be equivalent to Perylene Brilliant Red S-0499 in terms of color light; According to Table 3, the values ​​of brightness, redness, greenness, yellowness and blueness and color depth of Examples 1 to 4 are basically close to those of Perylene Brilliant Red S-0499, and the qualified value of ΔE* is between 1% and 2%; It shows that the tinting power of the CI Pigment Red 224 mixed crystal of the present application is close to that of Perylene Brilliant Red S-0499, and can be equivalent to Perylene Brilliant Red S-0499 in terms of tinting power. The present solution is based on low energy consumption, low material consumption and low pollution in the entire preparation process, with a high degree of recovery of solutions, filtrates, etc., mild and controllable reaction conditions, low degree of side reactions and high yield of target products. However, the traditional CI Pigment Red 224 has the problems of high energy consumption, high material consumption and high pollution during preparation, which means that the present application can replace CI Pigment Red 224 and overcome the problems of high energy consumption, high material consumption and high pollution faced in the traditional preparation of CI Pigment Red 224.

[0135] The above-mentioned embodiments only express several implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A method for preparing a CI Pigment Red 224 mixed crystal preformed solid, characterized in that: The following steps are involved: Step (1): adding the pigment mixed crystals to dilute sulfuric acid with a concentration of 40-70%, heating to 40-90°C under stirring, and continuously adding hydrogen peroxide; Pigment mixed crystals include: , and ; Step (2): Continue to raise the temperature to a reaction temperature not higher than 100° C., and stop heating after the reaction ends; Step (3): cooling and filtering, washing the product with water and filtering it, and drying it to obtain a CI Pigment Red 224 mixed crystal preformed solid; CI Pigment Red 224 mixed crystal preformed solid, by mass percentage, comprising: 90-97% 2-7% and the remainder ; Before step (1), step (S) is performed; step (S) comprises: Step (S1): under the protection of an inert gas, adding reaction raw material 1 and reaction raw material 2 to a reaction mixed solvent at a molar ratio of 1: (0.01-0.10); the reaction mixed solvent comprises the following components: an organic base and an organic solvent; Reaction material 1 is ; Reaction material 2 is ; Step (S2): heating to 150-200°C for reaction, and stopping heating after the reaction is completed; Step (S3): naturally cooling to room temperature, filtering after dilution, washing, and drying to obtain a dark red solid; the dark red solid is used as the pigment mixed crystal in step (1).

2. The method for preparing a CI Pigment Red 224 mixed crystal preformed solid according to claim 1, characterized in that: In the step (S1), the organic solvent is composed of the following components: o-dichlorobenzene and / or 1,2,4-trichlorobenzene; The organic base consists of at least one of 1,8-diazabicycloundec-7-ene, 2-(di-n-butyl)ethanolamine and 1,5-dioxabicyclo[4.3.0]non-5-ene.

3. The method for preparing a CI Pigment Red 224 mixed crystal preformed solid according to claim 1, characterized in that: In the step (S1), the preparation method of the reaction raw material 2 includes: Step (S1-1): under the protection of inert gas, add anhydrous ethanol into a reaction container, add 1,8-naphthalene anhydride and 3,5-xylidine under stirring, raise the temperature to reflux, and react for a period of time; Step (S1-2): tracking the reaction by silica gel thin plate chromatography (TLC), and stopping heating after the reaction is completed; Step (S1-3): naturally cool to room temperature and filter, wash the filter cake, and dry to obtain a pink reaction raw material 2.

4. The method for preparing a CI Pigment Red 224 mixed crystal preformed solid according to claim 3, characterized in that: Performing step (S4) after step (S3); Step (S4): The filtered mother liquor after filtering in step (S3) and the washing liquid after washing are subjected to reduced pressure distillation to recover the monohydric fatty alcohol and the reaction mixed solvent respectively.

5. A method for preparing a CI Pigment Red 224 mixed crystal, comprising the method for preparing a CI Pigment Red 224 mixed crystal preformed solid according to any one of claims 1 to 4, characterized in that: The CI Pigment Red 224 mixed crystal preformed solid obtained in step (3) is subjected to pigmentation processing.

6. The method for preparing a CI Pigment Red 224 mixed crystal according to claim 5, characterized in that: Pigmentation processing: The CI Pigment Red 224 mixed crystal preformed solid prepared in step (3) is added with an inorganic salt, an organic salt and a ball milling solvent, and transferred to a ball mill for ball milling, sieved to screen out steel balls, poured into hot water, stirred and filtered, the filter cake is washed with water until the conductivity of the filtrate is less than 300 microsiemens, and dried to obtain CI Pigment Red 224 mixed crystal; The mass ratios of CI Pigment Red 224 mixed crystal preformed solid, steel balls, inorganic salt, ball milling solvent and organic salt are: (1-30): (50-150): (15-25): (2-6):

1.

7. A CI Pigment Red 224 mixed crystal preformed solid, characterized in that: The CI Pigment Red 224 mixed crystal preformed solid is prepared by the preparation method of any one of claims 1 to 4.

8. A CI Pigment Red 224 mixed crystal, characterized in that The mixed crystal of CI Pigment Red 224 is prepared by the preparation method of the mixed crystal of CI Pigment Red 224 according to claim 5 or 6.

9. Use of a prefabricated solid in the preparation of a pigment having a color similar to that of CI Pigment Red 224, characterized in that: The preformed solid is prepared by the preparation method of a CI Pigment Red 224 mixed crystal preformed solid according to any one of claims 1 to 4.

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