Dioxazine compound, synthesis method and application of dioxazine compound as pigment

Abstract

The invention relates to the technical field of organic synthesis, in particular to a dioxazine compound, a synthesis method and application of the dioxazine compound as a pigment. The invention discloses a dioxazine compound, the dioxazine compound has a structure shown in a formula 1: # imgabs0 #, and R is selected from # imgabs1 #. The invention discloses the dioxazine compound, a synthesis method and application of the dioxazine compound as a pigment, the dioxazine compound prepared by adopting the method has good solubility, the dispersity of a blue pigment is greatly improved, and a pigmentation process is simplified.

Description

Technical Field

[0001] The present application relates to the technical field of organic synthesis, and in particular to a dioxazine compound, a synthesis method and an application thereof as a pigment. Background Art

[0002] With the rapid development of organic pigment application fields, such as various printing ink technologies, coatings industry with different characteristics of dispersion media, textile coating printing and dyeing, resin plastics and synthetic fiber coloring, and special functional coloring technologies, the demand for organic pigments as colorants has increased significantly, and the output has increased year by year. The increase in the scale of organic pigment production and the expansion of application fields have promoted the research and development of high-performance organic pigments with new chemical structures and excellent application performance, and at the same time improved the performance of existing pigment varieties.

[0003] The varieties of organic pigments include: special azo pigments, quinacridone pigments, perylene series pigments, carbazole or dioxazine pigments, isoindoline and isoindolinone, anthraquinone and quinophthalone pigments, pyrrolopyrrole dione pigments, copper phthalocyanine and high-grade phenol pigments, etc.; among them, copper phthalocyanine has poor antioxidant properties when used as an organic pigment, and contains metallic copper, which makes the polymer easy to degrade.

[0004] Therefore, it is urgent to prepare a pigment with good antioxidant properties and without metallic copper. Summary of the invention

[0005] In view of the deficiencies of the prior art, the present application provides a dioxazine compound, a synthesis method and an application thereof as a pigment.

[0006] The target product of this application is a high-grade blue organic pigment with a widely used dioxazine chemical structure, which is mainly used for outdoor high-grade coatings such as vehicles, plastics, engineering plastics, rubber and artificial fibers. It is characterized by being non-toxic, high temperature resistant (300°C), light fastness (8 levels), migration resistance (5 levels), and resistance to various solvents (5 levels). Since it does not contain metals that have a destructive effect on polymer materials, and is safe and non-toxic, and has good oxidation resistance, it has a very wide range of applications.

[0007] In the first aspect, the present application provides a dioxazine pigment, which adopts the following technical solution:

[0008] A dioxazine pigment having a structure as shown in Formula 1:

[0009]

[0010] Among them, R is selected from

[0011] In a second aspect, the present application provides a method for synthesizing a dioxazine compound, using the following technical solution:

[0012] A method for synthesizing a dioxazine compound, wherein the synthetic process route of the synthetic method is:

[0013]

[0014] Among them, R is selected from

[0015] X is selected from Cl, Br, I.

[0016] Preferably, the specific steps of the synthesis method are as follows:

[0017] (1) dissolving carbazole in a solvent, adding a halogenated cycloalkane, and reacting under the action of a phase transfer catalyst to obtain an N-cycloalkyl carbazole;

[0018] (2) dissolving N-cycloalkylcarbazole in a solvent, adding nitric acid to react, and obtaining 3-nitro-N-cycloalkylcarbazole;

[0019] (3) dissolving 3-nitro-N-cycloalkylcarbazole in a solvent and reacting with hydrogen in the presence of a catalyst to generate 3-amino-N-cycloalkylcarbazole;

[0020] (4) Under alkaline conditions, 3-amino-N-cycloalkylcarbazole is reacted with tetrachlorobenzoquinone to generate 2,5-dichloro-3,6-di{(9-cycloalkyl-3-iminocarbazole)}-1,4-benzoquinone, and then a ring-closing agent is added to react to obtain a dioxazine compound shown in Formula 1.

[0021] Preferably, the halogenated cycloalkane in step (1) is a chlorocycloalkane, a bromocycloalkane or an iodocycloalkane.

[0022] Preferably, the phase transfer catalyst in step (1) is benzyl-N-triethylammonium chloride.

[0023] Preferably, the reaction temperature in step (1) is 60°C-150°C.

[0024] Preferably, the solvent used in step (1) is a sodium hydroxide solution with a mass concentration of 40%.

[0025] Preferably, in step (1), the molar ratio of carbazole to halogenated cycloalkane is 1:(1-2); and the phase transfer catalyst is 1-2% of the total mass of carbazole and halogenated cycloalkane.

[0026] Preferably, the reaction temperature in step (2) is 25°C-50°C.

[0027] Preferably, the solvent used in step (2) is chlorobenzene.

[0028] Preferably, in step (2), the molar ratio of N-cycloalkylcarbazole to nitric acid is 1:(1-2).

[0029] Preferably, in step (3), the reaction temperature is 100° C.-150° C. and the reaction pressure is 0.1 MPa-10 MPa.

[0030] Preferably, the solvent used in step (3) is o-dichlorobenzene.

[0031] Preferably, the catalyst in step (3) is an active nickel catalyst.

[0032] Preferably, in step (3), the catalyst is 1-3% of the mass of 3-nitro-N-cycloalkylcarbazole; the molar ratio of 3-nitro-N-cycloalkylcarbazole to hydrogen is 1:(2-3).

[0033] Preferably, the ring-closing agent in step (4) is benzenesulfonyl chloride; and the base used in step (4) is triethylamine.

[0034] Preferably, the temperature for reacting the ring-closing agent in step (4) is 150° C.-180° C., and the reaction time is 3-10 hours.

[0035] Preferably, the temperature for reacting 3-amino-N-cycloalkylcarbazole and tetrachlorobenzoquinone in step (4) is 30°C-100°C.

[0036] Preferably, in step (4), the molar ratio of 3-amino-N-cycloalkylcarbazole to tetrachlorobenzoquinone and base is (1.6-1.8):1:(2-2.1).

[0037] Preferably, in step (4), the mass ratio of 2,5-dichloro-3,6-di{(9-cycloalkyl-3-iminocarbazole)}-1,4-benzoquinone to the ring-closing agent is 2:1.

[0038] In a third aspect, the present application provides an application of a dioxazine compound in a pigment preparation process, using the following technical solution:

[0039] Application of the above dioxazine compound or the dioxazine compound prepared by the above method in the pigment preparation process.

[0040] In a specific embodiment, a method for preparing a dioxazine pigment is as follows:

[0041] Carbazole is used as the initial raw material, and a halogenated cycloalkane (chlorocycloalkane, bromocycloalkane or iodocycloalkane) is added to a sodium hydroxide aqueous solution with a mass concentration of 40%. Under the action of a phase transfer catalyst (benzyl-N-triethylammonium chloride) at 60-150° C., the corresponding N-cycloalkyl carbazole is generated, and then pure N-cycloalkyl carbazole is obtained through layer separation.

[0042]

[0043] Among them, R is selected from

[0044] X is selected from Cl, Br, I.

[0045] N-cycloalkylcarbazole is reacted with nitric acid having a mass concentration of 35-40% at 25°C-50°C in a solvent (chlorobenzene) to generate corresponding 3-nitro-N-cycloalkylcarbazole, and then pure 3-nitro-N-cycloalkylcarbazole is obtained through separation.

[0046]

[0047] Among them, R is selected from

[0048] 3-Nitro-N-cycloalkylcarbazole reacts with hydrogen in a solvent (o-dichlorobenzene) at 100-150° C., 0.1-10 MPa pressure and in the presence of a catalyst (active nickel catalyst) to generate 3-amino-N-cycloalkylcarbazole.

[0049]

[0050] Among them, R is selected from

[0051] At 30°C-100°C, under alkaline (triethylamine) conditions, 3-amino-N-cycloalkylcarbazole reacts with tetrachlorobenzoquinone to generate 2,5-dichloro-3,6-di{(9-cycloalkyl-3-iminocarbazole)}-1,4-benzoquinone, a ring-closing agent (benzenesulfonyl chloride) is added, and the reaction is carried out at 150-180°C for 3-10 hours to generate a blue crude pigment (hereinafter referred to as the crude product). After filtering, high-temperature solvent washing, alcohol washing, water washing, drying and crushing, a blue powdery crude pigment is obtained, namely, the dioxazine compound shown in Formula 1.

[0052]

[0053] Among them, R is selected from

[0054] In summary, the present application includes at least one of the following beneficial technical effects:

[0055] The present application discloses a dioxazine compound, a synthesis method and an application thereof as a pigment. The dioxazine compound prepared by the method of the present application has good solubility, greatly improves the dispersibility of the blue pigment and simplifies the pigmentation process.

[0056] The dioxazine compound prepared by the method of the present application does not contain metals that are destructive to polymer materials and is safe and non-toxic, so it has a wide range of applications.

[0057] The preparation method provided in the present application is simple in process, easy to operate and easy to promote. DETAILED DESCRIPTION

[0058] The technical solution of the present application is further illustrated by specific embodiments below. The specific embodiments do not limit the protection scope of the present application; some non-essential modifications and adjustments made by others based on the concept of the present application still fall within the protection scope of the present application.

[0059] The raw materials involved in this application are all commercially available products.

[0060] The present application is further described in detail below in conjunction with embodiments and comparative examples.

[0061] Example 1: Preparation of N-cyclopropylcarbazole

[0062] In a 1000 ml three-necked flask equipped with a stirrer, thermometer and condenser, 300 g of 40% sodium hydroxide aqueous solution, 100 g of 100% carbazole, 3 g of benzyl-N-triethylammonium chloride and 80 g of bromocyclopropane were added in sequence, and the temperature was raised to 120°C under stirring, and the mixture was kept warm and stirred for 3 hours. The sample was taken for liquid chromatography analysis. When the carbazole residue was ≤1‰, the reaction was terminated (if it was >1‰, the reaction was continued), and the unreacted bromocyclopropane was distilled out. The stirring was stopped, and the mixture was kept warm and allowed to stand for 2 hours. The supernatant (N-cyclopropylcarbazole) was taken out to obtain about 120 g of the product. The specific chemical reaction formula is as follows:

[0063]

[0064] Example 2: N-cyclobutylcarbazole

[0065] In a 1000 ml three-necked flask equipped with a stirrer, thermometer and condenser, 300 g of 40% sodium hydroxide aqueous solution, 100 g of 100% carbazole, 3 g of benzyl-N-triethylammonium chloride and 90 g of bromocyclobutane were added in sequence, the temperature was raised to 120°C under stirring, and the mixture was kept warm and stirred for 3 hours. The sample was taken for liquid chromatography analysis. When the carbazole residue was ≤1‰, the reaction was terminated (if >1‰, the reaction was continued), the unreacted bromocyclobutane was distilled out, the stirring was stopped, the mixture was kept warm and allowed to stand for 2 hours, and the supernatant (N-cyclobutylcarbazole) was taken out to obtain about 132 g of the product. The specific chemical reaction formula is as follows:

[0066]

[0067] Example 3: N-cyclopentylcarbazole

[0068] In a 1000 ml three-necked flask equipped with a stirrer, thermometer and condenser, add 300 g of 40% sodium hydroxide aqueous solution, 100 g of 100% carbazole, 3 g of benzyl-N-triethylammonium chloride and 100 g of bromocyclopentane in sequence, heat to 125°C under stirring, keep warm and stir for 3 hours, take samples for liquid chromatography analysis, end the reaction when the carbazole residue is ≤1‰ (if >1‰, continue the reaction), distill out the unreacted bromocyclopentane, stop stirring and keep warm for 2 hours, take out the supernatant (N-cyclopentylcarbazole), and obtain about 140 g of the product. The specific chemical reaction formula is as follows:

[0069]

[0070] Example 4: N-cyclohexylcarbazole

[0071] In a 1000 ml three-necked flask equipped with a stirrer, thermometer and condenser, add 300 g of 40% sodium hydroxide aqueous solution, 100 g of 100% carbazole, 3 g of benzyl-N-triethylammonium chloride and 110 g of bromocyclohexane in sequence, heat to 125°C under stirring, keep warm and stir for 3 hours, take samples for liquid chromatography analysis, end the reaction when the carbazole residue is ≤1‰ (if >1‰, continue the reaction), distill out the unreacted bromocyclohexane, stop stirring and keep warm for 2 hours, take out the supernatant (N-cyclohexylcarbazole), and obtain about 149 g of the product. The specific chemical reaction formula is as follows:

[0072]

[0073] Example 5: Preparation of 3-nitro-9-cyclopropylcarbazole

[0074] In a 1000 ml three-necked flask equipped with a thermometer and agitator, 100 g of the product N-cyclopropylcarbazole of Example 1 and 200 g of chlorobenzene were added in sequence, stirred and heated to 60°C, and after N-cyclopropylcarbazole was completely dissolved, 130 g of nitric acid with a volume concentration of 40% was added dropwise over 120-180 minutes. After the addition was completed, the mixture was kept warm and stirred for 120 minutes at 30°C. The mixture was cooled to 0-5°C with a salt ice water bath, kept warm and stirred at a low speed for 2 hours, and filtered. The material in the three-necked flask was washed with 50 ml of 0°C chlorobenzene in the filter cake, and the filter cake was washed with 500 ml of a 30°C aqueous solution containing 1% of the mass concentration of pull-open powder BX, and the filter cake was washed with pure water until the pH was ≥6, the filter cake was removed, and dried at 70°C to obtain 103.5 g of the product with a yield of 85%. The specific chemical reaction formula is as follows:

[0075]

[0076] Example 6: Preparation of 3-nitro-9-cyclopentylcarbazole

[0077] In a 1000 ml three-necked flask equipped with a thermometer and a stirrer, 100 g of the product N-cyclopentylcarbazole of Example 3 and 250 g of chlorobenzene were added in sequence, stirred and heated to 65°C, and after N-cyclopentylcarbazole was completely dissolved, 114 g of nitric acid with a volume concentration of 40% was added dropwise over 120-180 minutes. After the addition was completed, the mixture was kept warm and stirred for 120 minutes at 30°C. The mixture was cooled to 0-5°C with a salt ice water bath, kept warm and stirred at a low speed for 2 hours, and filtered with a heat preservation temperature. The material in the three-necked flask was washed with 50 ml of 0°C chlorobenzene in the filter cake, and the filter cake was washed with 500 ml of a 30°C aqueous solution containing 1% of the mass concentration of pull-open powder BX, and the filter cake was washed with pure water until the pH was ≥6, the filter cake was removed, and dried at 70°C to obtain 102.5 g of the product with a yield of 86%. The specific chemical reaction formula is as follows:

[0078]

[0079] Example 7: Preparation of 3-nitro-9-cyclohexylcarbazole

[0080] In a 1000 ml three-necked flask equipped with a thermometer and agitator, 100 g of the product N-cyclohexylcarbazole of Example 4 and 300 g of chlorobenzene were added in sequence, stirred and heated to 65°C, and after N-cyclohexylcarbazole was completely dissolved, 108 g of nitric acid with a volume concentration of 40% was added dropwise over 120-180 minutes, and after the addition was completed, the mixture was kept warm and stirred for 120 minutes at 30°C. The mixture was cooled to 0-5°C with a salt ice water bath, kept warm and stirred at a low speed for 2 hours, and filtered with a heat preservation temperature. The material in the three-necked flask was washed with 50 ml of 0°C chlorobenzene in the filter cake, and the filter cake was washed with 500 ml of a 30°C aqueous solution containing 1% of the mass concentration of pull-open powder BX, and the filter cake was washed with pure water until the pH was ≥6, the filter cake was removed, and dried at 70°C to obtain 101.5 g of the product with a yield of 86%. The specific chemical reaction formula is as follows:

[0081]

[0082] Example 8: Preparation of 3-amino-9-cyclopropylcarbazole

[0083] In a 1000 ml autoclave, add 100 g of the product 3-nitro-9-cyclopropylcarbazole of Example 5, 500 g of o-dichlorobenzene, and 2 g of active nickel catalyst in sequence. The autoclave is closed, vacuum nitrogen is replaced 3 times, the temperature is raised to 150°C, and hydrogen is introduced at the same time. The pressure in the autoclave is up to 1.5 MPa, and the hydrogen rate is controlled according to the reaction rate during the entire hydrogenation. After the reaction is completed, the temperature is lowered to 25°C at room temperature, the pressure is released to normal pressure, and the material is moved into a 1000 ml beaker to separate the catalyst and water to obtain a 3-amino-9-cyclopropylcarbazole o-dichlorobenzene solution containing 88 g of 3-amino-9-cyclopropylcarbazole. The specific chemical reaction formula is as follows:

[0084]

[0085] Example 9: Preparation of 3-amino-9-cyclopentylcarbazole

[0086] In a 1000 ml autoclave, add 100 g of the product 3-nitro-9-cyclopentylcarbazole of Example 6, 500 g of o-dichlorobenzene, and 2 g of active nickel catalyst in sequence. Close the autoclave and replace it with vacuum nitrogen three times. Heat up to 150°C and introduce hydrogen at the same time. The pressure in the autoclave is up to 1.5 MPa. The hydrogen rate is controlled according to the reaction rate during the entire hydrogenation. After the reaction is completed, cool to room temperature 25°C, release the pressure to normal pressure, move the material into a 1000 ml beaker to separate the catalyst and water, and obtain a 3-amino-9-cyclopentylcarbazole o-dichlorobenzene solution containing 89 g of 3-amino-9-cyclopentylcarbazole. The specific chemical reaction formula is as follows:

[0087]

[0088] Example 10: Preparation of 3-amino-9-cyclohexylcarbazole

[0089] In a 1000 ml autoclave, add 100 g of the product 3-nitro-9-cyclohexylcarbazole of Example 7, 500 g of o-dichlorobenzene, and 2 g of active nickel catalyst in sequence. Close the autoclave and replace it with vacuum nitrogen three times. Heat to 150°C and introduce hydrogen at the same time. The pressure in the autoclave is up to 1.5 MPa. The hydrogen rate is controlled according to the reaction rate during the entire hydrogenation. After the reaction is completed, cool to room temperature 25°C, release the pressure to normal pressure, move the material into a 1000 ml beaker to separate the catalyst and water, and obtain a 3-amino-9-cyclohexylcarbazole o-dichlorobenzene solution containing 89.8 g of 3-amino-9-cyclohexylcarbazole. The specific chemical reaction formula is as follows:

[0090]

[0091] Example 11: Preparation of dioxazine compound 1

[0092] In a 3000 ml three-necked flask equipped with a condenser, a thermometer and a stirrer, the 3-amino-9-cyclopropylcarbazole o-dichlorobenzene solution of Example 8 was added, the volume was adjusted to 2000 ml with o-dichlorobenzene, the temperature was adjusted to 40°C, 45 g of triethylamine was added under stirring, the stirring was stopped, 53.6 g of tetrachlorobenzoquinone was quickly added, and the stirring was turned to a high speed position for condensation reaction. After 5 minutes, the temperature automatically rose to 68°C. If it could not be heated to 70°C, the reaction was stirred and kept warm for 120 minutes to obtain 100 g of 2,5-dichloro-3,6-bis(9-cyclopropyl-3-iminocarbazole)-1,4-benzoquinone.

[0093] Continue to raise the temperature to 140°C, add 50 g of benzenesulfonyl chloride, raise the temperature to reflux state within 10 minutes, the temperature is 175°C, keep stirring and react for 300 minutes, cool to 130°C, filter with a Buchner funnel, wash the three-necked flask and the filter cake with 1000 ml of o-dichlorobenzene at 130°C, then wash the filter cake with 200 ml of room temperature o-dichlorobenzene, wash the filter cake again with 200 ml of ethanol, and finally wash the filter cake with 2000 ml of pure water, drain, and dry the filter cake at 100°C to obtain 106.9 g of crude pigment blue 1 (dioxazine compound 1) with a yield of 88%.

[0094]

[0095] Example 12: Preparation of dioxazine compound 2

[0096] In a 3000 ml three-necked flask equipped with a condenser, a thermometer and a stirrer, the 3-amino-9-cyclopentylcarbazole o-dichlorobenzene solution of Example 9 was added, the volume was adjusted to 2000 ml with o-dichlorobenzene, the temperature was adjusted to 40°C, 42 g of triethylamine was added under stirring, the stirring was stopped, 48.1 g of tetrachlorobenzoquinone was quickly added, and the stirring was turned to a high speed position for condensation reaction. After 5 minutes, the temperature automatically rose to 68°C. If it could not be heated to 70°C, the reaction was stirred for 120 minutes under heat preservation to obtain 90 g of 2,5-dichloro-3,6-di(9-cyclopentyl-3-iminocarbazole)-1,4-benzoquinone.

[0097] Continue to raise the temperature to 140°C, add 45 g of benzenesulfonyl chloride, raise the temperature to reflux state within 10 minutes, the temperature is 175°C, keep stirring and react for 300 minutes, cool to 130°C, filter with a Buchner funnel, wash the three-necked flask and the filter cake with 1000 ml of o-dichlorobenzene at 130°C, then wash the filter cake with 200 ml of room temperature o-dichlorobenzene, wash the filter cake again with 200 ml of ethanol, and finally wash the filter cake with 2000 ml of pure water, drain, and dry the filter cake at 100°C to obtain 104.8 g of crude pigment blue 2 (dioxazine compound 2) with a yield of 88%.

[0098]

[0099] Example 13: Preparation of dioxazine compound 3

[0100] In a 3000 ml three-necked flask equipped with a condenser, a thermometer and a stirrer, the 3-amino-9-cyclohexylcarbazole o-dichlorobenzene solution of Example 10 was added, the volume was adjusted to 2000 ml with o-dichlorobenzene, the temperature was adjusted to 40°C, 38 g of triethylamine was added under stirring, the stirring was stopped, 46.1 g of tetrachlorobenzoquinone was quickly added, and the stirring was turned to a high speed position for condensation reaction. After 5 minutes, the temperature automatically rose to 68°C. If it could not be heated to 70°C, the reaction was stirred and kept warm for 120 minutes to obtain 84 g of 2,5-dichloro-3,6-di(9-cyclohexyl-3-iminocarbazole)-1,4-benzoquinone.

[0101] Continue to raise the temperature to 140°C, add 42 g of benzenesulfonyl chloride, raise the temperature to reflux state within 10 minutes, the temperature is 175°C, keep stirring and react for 300 minutes, cool to 130°C, filter with a Buchner funnel, wash the three-necked flask and the filter cake with 1000 ml of o-dichlorobenzene at 130°C, then wash the filter cake with 200 ml of room temperature o-dichlorobenzene, wash the filter cake again with 200 ml of ethanol, and finally wash the filter cake with 2000 ml of pure water, drain, and dry the filter cake at 100°C to obtain 100.8 g of crude pigment blue 3 (dioxazine compound 3) with a yield of 85%.

[0102]

[0103] Example 14: Acid-soluble pigmentation

[0104] In a 500 ml three-necked flask equipped with a thermometer and stirrer, add 500 g of 95% by volume concentrated sulfuric acid, slowly add 50 g of the crude product of Example 11 over 50-60 minutes at a temperature of ≤25°C, and stir for 4 hours. Then dilute the solution in 3000 ml of ice water over 15-20 minutes, keep the temperature at ≤25°C, stir for 120 minutes, filter, wash with pure water until the pH is ≥6.0, dry at 60°C, and crush to obtain the finished pigment.

[0105] Product features: fine crystal particles and good transparency.

[0106] Example 15: Acid-soluble pigmentation

[0107] In a 500 ml three-necked flask equipped with a thermometer stirrer, add 500 g of concentrated sulfuric acid with a volume concentration of 95%, slowly add 50 g of the crude product of Example 12 at a temperature of ≤25°C over 50-60 minutes, and stir at this temperature for 4 hours. Then dilute the solution in 3000 ml of water over 15-20 minutes, keep the temperature at ≤50°C, stir at this temperature for 60 minutes, heat to 90°C and stir at this temperature for 120 minutes, filter, wash with pure water until the pH is ≥6.0, dry at 60°C, pulverize, and obtain the finished pigment.

[0108] Product features: The crystal particles are slightly coarse and have good covering power.

[0109] Example 16: Acid-dissolved eutectic crystal method for pigmentation

[0110] In a 500 ml three-necked flask equipped with a thermometer and stirrer, add 500 g of 95% by volume concentrated sulfuric acid, slowly add 25 g of the crude product of Example 11 and 25 g of the crude product of Example 12 at a temperature of ≤25°C over 50-60 minutes, and stir for 4 hours. Then dilute the solution in 3000 ml of ice water over 15-20 minutes, keep the temperature at ≤25°C, stir for 120 minutes, filter, wash with pure water until the pH is ≥6.0, dry at 60°C, and pulverize to obtain the finished pigment.

[0111] Product features: fine crystal particles and good transparency.

[0112] Example 17: Acid-dissolved eutectic crystal method for pigmentation

[0113] In a 500 ml three-necked flask equipped with a thermometer and stirrer, add 500 g of 95% by volume concentrated sulfuric acid, slowly add 25 g of the crude product of Example 11 and 25 g of the crude product of Example 13 over 50-60 minutes at a temperature of ≤25°C, and stir for 4 hours. Then dilute the solution in 3000 ml of ice water over 15-20 minutes, keep the temperature at ≤25°C, stir for 120 minutes, filter, wash with pure water until the pH is ≥6.0, dry at 60°C, pulverize, and obtain the finished pigment.

[0114] Product features: fine crystal particles and good transparency.

[0115] Example 18: Pigmentation by Acid-Dissolving Eutectic Crystal Method

[0116] In a 500 ml three-necked flask equipped with a thermometer and stirrer, add 500 g of concentrated sulfuric acid with a volume concentration of 95%, slowly add 45 g of the crude product of Example 10 and 5 g of the crude product of Example 11 over 50-60 minutes at a temperature of ≤25°C, and stir for 4 hours. Then dilute the solution in 3000 ml of ice water over 15-20 minutes, keep the temperature at ≤25°C, stir for 120 minutes, filter, wash with pure water until the pH is ≥6.0, dry at 60°C, and crush to obtain the finished pigment.

[0117] Product features: fine crystal particles and good transparency.

[0118] Example 19: Pigmentation by Acid-Dissolving Eutectic Crystal Method

[0119] In a 500 ml three-necked flask equipped with a thermometer and stirrer, add 500 g of concentrated sulfuric acid with a volume concentration of 95%, slowly add 45 g of the crude product of Example 10 and 5 g of the crude product of Example 12 over 50-60 minutes at a temperature of ≤25°C, and stir for 5 hours. Then dilute the solution in 3000 ml of ice water over 15-20 minutes, keep the temperature at ≤25°C, stir for 120 minutes, filter, wash with pure water until the pH is ≥6.0, dry at 60°C, and crush to obtain the finished pigment.

[0120] Product features: fine crystal particles and good transparency.

[0121] Example 20: Pigmentation by Acid-Dissolving Eutectic Crystal Method

[0122] In a 500 ml three-necked flask equipped with a thermometer and stirrer, add 500 g of 95% by volume concentrated sulfuric acid, slowly add 45 g of the crude product of Example 11 and 5 g of the crude product of Example 12 over 50-60 minutes at a temperature of ≤25°C, and stir for 5 hours. Then dilute the solution in 3000 ml of ice water over 15-20 minutes, keep the temperature at ≤25°C, stir for 120 minutes, filter, wash with pure water until the pH is ≥6.0, dry at 60°C, and pulverize to obtain the finished pigment.

[0123] Product features: fine crystal particles and good transparency.

[0124] Example 21: Pigmentation by Acid-Dissolving Eutectic Crystal Method

[0125] In a 500 ml three-necked flask equipped with a thermometer stirrer, add 500 g of concentrated sulfuric acid with a volume concentration of 95%, slowly add 45 g of the crude product of Example 10, 2.5 g of the crude product of Example 11, and 2.5 g of the crude product of Example 12 over 50-60 minutes at a temperature of ≤25°C, and stir for 5 hours. Then dilute the solution in 3000 ml of ice water over 15-20 minutes, keep the temperature at ≤25°C, stir for 120 minutes, filter, wash with pure water until the pH is ≥6.0, dry at 60°C, pulverize, and obtain the finished pigment.

[0126] Product features: fine crystal particles and good transparency.

[0127] Example 22: Kneading method pigmentation

[0128] Into a kneader with a capacity of 2000 ml, add 50 g of the crude product of Example 11, 500 g of fine salt, and 90 g of diethylene glycol in sequence, start stirring and heat to 110°C, keep warm and knead for 8 hours, transfer the paste into a 3000 ml beaker, add 2300 ml of pure water and 200 g of 30% hydrochloric acid by volume, stir and beat until there is no lumps, heat to 85°C, keep warm and stir for 120 minutes, cool to 70°C, filter and wash until the water is ≥6 and the chloride ion meets the standard. Dry at 60°C and crush to obtain the finished pigment.

[0129] Product features: The crystal particles are uniform and the transparency is average.

[0130] Example 23: Kneading method pigmentation

[0131] Into a kneader with a capacity of 2000 ml, add 50 g of the crude product of Example 12, 500 g of fine salt, and 90 g of diethylene glycol in sequence, start stirring and heat to 90°C, keep warm and knead for 8 hours, transfer the paste into a 3000 ml beaker, add 2300 ml of pure water and 200 g of 30% hydrochloric acid by volume, stir and beat until there is no lumps, heat to 85°C, keep warm and stir for 120 minutes, cool to 70°C, filter and wash until the water is ≥6 and the chloride ion meets the standard. Dry at 60°C and crush to obtain the finished pigment.

[0132] Product features: The crystal particles are uniform and the transparency is slightly better.

[0133] Example 24: Pigmentation by kneading eutectic method

[0134] In a kneader with a capacity of 2000 ml, add 45 g of the crude product of Example 11, 5 g of the crude product of Example 12, 500 g of fine salt, and 90 g of diethylene glycol in sequence, start stirring and heat to 110°C, keep warm and knead for 8 hours, transfer the paste into a 3000 ml beaker, add 2300 ml of pure water and 200 g of 30% hydrochloric acid by volume, stir and beat until there is no lumps, heat to 85°C, keep warm and stir for 120 minutes, cool to 70°C, filter and wash until the water is ≥6 and the chloride ion meets the standard. Dry at 60°C and crush to obtain the finished pigment.

[0135] Product features: The crystal particles are uniform and have good transparency.

[0136] Example 25: Pigmentation by kneading eutectic method

[0137] In a kneader with a capacity of 2000 ml, add 45 g of the crude product of Example 12, 5 g of the crude product of Example 13, 500 g of fine salt, and 90 g of diethylene glycol in sequence, start stirring and heat to 90°C, keep warm and knead for 8 hours, transfer the paste into a 3000 ml beaker, add 2300 ml of pure water and 200 g of 30% hydrochloric acid by volume, stir and beat until there is no lumps, heat to 85°C, keep warm and stir for 120 minutes, cool to 70°C, filter and wash until the water is ≥6 and the chloride ion meets the standard. Dry at 60°C and crush to obtain the finished pigment.

[0138] Product features: The crystal particles are uniform and have good transparency.

[0139] Example 26: Pigmentation by kneading eutectic method

[0140] In a kneader with a capacity of 2000 ml, add 45 g of the crude product of Example 10, 5 g of the crude product of Example 13, 500 g of fine salt, and 90 g of diethylene glycol in sequence, start stirring and heat to 100°C, keep warm and knead for 8 hours, transfer the paste into a 3000 ml beaker, add 2300 ml of pure water and 200 g of 30% hydrochloric acid by volume, stir and beat until there is no lumps, heat to 85°C, keep warm and stir for 120 minutes, cool to 70°C, filter and wash until the water concentration is ≥6 and the chloride ion meets the standard. Dry at 60°C and crush to obtain the finished pigment.

[0141] Product features: The crystal particles are uniform and have good transparency.

[0142] Example 27: Pigmentation by kneading eutectic crystal method

[0143] In a kneader with a capacity of 2000 ml, add 40 g of the crude product of Example 11, 10 g of the crude product of Example 12, 500 g of fine salt, and 90 g of diethylene glycol in sequence, start stirring and heat to 110°C, keep warm and knead for 8 hours, transfer the paste into a 3000 ml beaker, add 2300 ml of pure water and 200 g of 30% hydrochloric acid by volume, stir and beat until there is no lumps, heat to 85°C, keep warm and stir for 120 minutes, cool to 70°C, filter and wash until the water is ≥6 and the chloride ion meets the standard. Dry at 60°C and crush to obtain the finished pigment.

[0144] Product features: The crystal particles are uniform and have good transparency.

[0145] Example 28: Pigmentation by kneading eutectic crystal method

[0146] In a kneader with a capacity of 2000 ml, add 40 g of the crude product of Example 11, 5 g of the crude product of Example 12, 5 g of the crude product of Example 13, 500 g of fine salt, and 90 g of diethylene glycol in sequence, start stirring and heat to 110°C, keep warm and knead for 8 hours, transfer the paste into a 3000 ml beaker, add 2300 ml of pure water and 200 g of 30% hydrochloric acid by volume, stir and beat until there is no lumps, heat to 85°C, keep warm and stir for 120 minutes, cool to 70°C, filter and wash until the water is ≥6 and the chloride ion meets the standard. Dry at 60°C and crush to obtain the finished pigment.

[0147] Product features: The crystal particles are uniform and the transparency is very good.

[0148] Example 29: Pigmentation by kneading eutectic method

[0149] In a kneader with a capacity of 2000 ml, add 45 g of the crude product of Example 11, 2.5 g of the crude product of Example 12, 2.5 g of the crude product of Example 13, 500 g of fine salt, and 90 g of diethylene glycol in sequence, start stirring and heat to 110°C, keep warm and knead for 8 hours, transfer the paste into a 3000 ml beaker, add 2300 ml of pure water and 200 g of 30% hydrochloric acid by volume, stir and beat until there is no lumps, heat to 85°C, keep warm and stir for 120 minutes, cool to 70°C, filter and wash until the water is ≥6 and the chloride ion meets the standard. Dry at 60°C and crush to obtain the finished pigment.

[0150] Product features: The crystal particles are uniform and have good transparency.

[0151] Example 30: Pigmentation by ball milling

[0152] Into a 3000 ml vertical ball mill, 1000 g of φ6 steel balls, 50 g of the crude product of Example 11, 300 g of anhydrous calcium chloride, and 20 ml of xylene were added in sequence, the jacket was passed through circulating water, and the stirring ball mill was started for 5 hours. The powder was transferred to a 3000 ml beaker, 2000 ml of water and 200 ml of 30% volume concentration hydrochloric acid were added, stirred and heated to 85°C, kept warm and stirred for 120 minutes, filtered, washed with water until pH ≥ 6.0 and the chloride ion reached the standard, the filter cake was dried and pulverized to obtain a finished pigment.

[0153] Product features: moderate transparency and high tinting strength.

[0154] Example 31: Pigmentation by ball milling

[0155] Into a 3000 ml vertical ball mill, 1000 g of φ6 steel balls, 50 g of the crude product of Example 12, 300 g of anhydrous calcium chloride, and 20 ml of xylene were added in sequence, the jacket was passed through circulating water, and the stirring ball mill was started for 5 hours. The powder was moved into a 3000 ml beaker, 2000 ml of water and 200 ml of 30% volume concentration hydrochloric acid were added, stirred and heated to 85°C, kept warm and stirred for 120 minutes, filtered, washed with water until pH ≥ 6.0 and the chloride ion reached the standard, the filter cake was dried and pulverized to obtain a finished pigment.

[0156] Product features: moderate transparency and high tinting strength.

[0157] Example 32: Pigmentation by eutectic ball milling

[0158] Into a 3000 ml vertical ball mill, 1000 g of φ6 steel balls, 40 g of the crude product of Example 11, 10 g of the crude product of Example 12, 300 g of anhydrous calcium chloride, and 20 ml of xylene were added in sequence, the jacket was passed through circulating water, and the stirring ball mill was started for 5 hours. The powder was moved into a 3000 ml beaker, 2000 ml of water and 200 ml of 30% by volume hydrochloric acid were added, stirred and heated to 85°C, kept warm and stirred for 120 minutes, filtered, washed with water until pH ≥ 6.0 and the chloride ion reached the standard, the filter cake was dried and pulverized to obtain a finished pigment.

[0159] Product features: moderate transparency and high tinting strength.

[0160] Example 33: Pigmentation by eutectic ball milling

[0161] Into a 3000 ml vertical ball mill, 1000 g of φ6 steel balls, 40 g of the crude product of Example 11, 5 g of the crude product of Example 12, 5 g of the crude product of Example 13, 300 g of anhydrous calcium chloride, and 20 ml of xylene were added in sequence, the jacket was passed through circulating water, and the stirring ball mill was started for 5 hours. The powder was moved into a 3000 ml beaker, 2000 ml of water and 200 ml of 30% by volume hydrochloric acid were added, stirred and heated to 85°C, kept warm and stirred for 120 minutes, filtered, washed with water until pH ≥ 6.0 and the chloride ion reached the standard, the filter cake was dried and pulverized to obtain a finished pigment.

[0162] Product features: moderate transparency and high tinting strength.

[0163] Application examples:

[0164] Polycarbonate plastics are inherently oxidizing, and phthalocyanine pigments used as colorants fade during the processing of polycarbonate plastics. When the products prepared in Examples 14 to 33 of the present application are used as colorants during the processing of polycarbonate plastics, no fading occurs during the processing.

[0165] Phthalocyanine pigments are used as colorants for polyethylene plastics. After being placed for half a year, the polyethylene plastic products will be powdered. The products prepared in Examples 14 to 33 of the present application are used as colorants to prepare polyethylene plastics. After being placed for half a year, the polyethylene plastic products will not be powdered.

[0166] The high-grade blue organic pigment with dioxazine chemical structure prepared in this application is mainly used for outdoor high-grade coatings such as vehicles, plastics, engineering plastics, rubber and artificial fibers, etc. It is characterized by being non-toxic, high temperature resistant (300°C), light fastness (8 levels), migration resistance (5 levels), and resistance to various solvents (5 levels). Since it does not contain metals that have a destructive effect on polymer materials and is safe and non-toxic, it has a wide range of applications.

Claims

1. A dioxazine compound, characterized in that: It has a structure as shown in Formula 1: Among them, R is selected from 2. A method for synthesizing a dioxazine compound, characterized in that: The synthetic process route of the synthetic method is: Among them, R is selected from X is selected from Cl, Br, I.

3. The synthesis method according to claim 2, characterized in that The specific steps of the synthetic method are as follows: (1) dissolving carbazole in a solvent, adding a halogenated cycloalkane, and reacting under the action of a phase transfer catalyst to obtain N-cycloalkylcarbazole; (2) dissolving N-cycloalkylcarbazole in a solvent, adding nitric acid to react, and obtaining 3-nitro-N-cycloalkylcarbazole; (3) dissolving 3-nitro-N-cycloalkylcarbazole in a solvent and reacting with hydrogen in the presence of a catalyst to generate 3-amino-N-cycloalkylcarbazole; (4) Under alkaline conditions, 3-amino-N-cycloalkylcarbazole is reacted with tetrachlorobenzoquinone to generate 2,5-dichloro-3,6-di{(9-cycloalkyl-3-iminocarbazole)}-1,4-benzoquinone, and then a ring-closing agent is added to react to obtain a dioxazine compound shown in Formula 1.

4. The synthesis method according to claim 3, characterized in that: In the step (1), the halogenated cycloalkane is a chlorocycloalkane, a bromocycloalkane or an iodocycloalkane; The phase transfer catalyst in step (1) is benzyl-N-triethylammonium chloride; The solvent used in the step (1) is a sodium hydroxide solution with a mass concentration of 40%.

5. The synthesis method according to claim 3, characterized in that: The solvent used in the step (2) is chlorobenzene.

6. The synthesis method according to claim 3, characterized in that: The solvent used in step (3) is o-dichlorobenzene; The catalyst in step (3) is an active nickel catalyst.

7. The synthesis method according to claim 3, characterized in that: In the step (4), the ring-closing agent is benzenesulfonyl chloride; The base used in step (4) is triethylamine.

8. The synthesis method according to claim 3, characterized in that: The reaction temperature in step (1) is 60°C-150°C; The reaction temperature in step (2) is 25°C-50°C; In step (3), the reaction temperature is 100° C.-150° C. and the reaction pressure is 0.1 MPa-10 MPa; The temperature for adding the ring-closing agent to react in step (4) is 150°C-180°C, and the reaction time is 3-10 hours; In the step (4), the temperature for reacting 3-amino-N-cycloalkylcarbazole with tetrachlorobenzoquinone is 30° C.-100° C.

9. The synthesis method according to claim 3, characterized in that: In the step (1), the molar ratio of carbazole to halogenated cycloalkane is 1:(1-2); In the step (1), the phase transfer catalyst is 1-2% of the total mass of carbazole and halogenated cycloalkane; In the step (2), the molar ratio of N-cycloalkylcarbazole to nitric acid is 1:(1-2); In the step (3), the catalyst is 1-3% of the mass of 3-nitro-N-cycloalkylcarbazole; In the step (3), the molar ratio of 3-nitro-N-cycloalkylcarbazole to hydrogen is 1:(2-3); In the step (4), the molar ratio of 3-amino-N-cycloalkylcarbazole to chloranil and base is (1.6-1.8):1:(2-2.1); In the step (4), the mass ratio of 2,5-dichloro-3,6-di{(9-cycloalkyl-3-iminocarbazole)}-1,4-benzoquinone to the ring-closing agent is 2:

1.

10. Use of the dioxazine compound according to claim 1 or the dioxazine compound prepared by the method according to any one of claims 2 to 9 in a pigment preparation process.

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