Dioxazine compound, synthetic method and application

Abstract

The invention relates to the technical field of dioxazine pigments, in particular to a dioxazine compound, a synthesis method and application. The invention relates to a dioxazine compound, which has a structure as shown in a formula 1: # imgabs0 #, in which R1, R2, R3, R4 and R5 are independently selected from H, CH3, C2H5, CH2CH2CH3, CH3CHCHCH3, CH2CH2CH2CH3, CH3CH2CHCH3, OCH3, OCH2CH3, OCH2CH2CH3, OCH3CHCH2CH3 and OCCH3CH3CH3, and in which R1, R2, R3, R4 and R5 are independently selected from H, CH3, C2H5, CH2CH2CH2CH3, CH2CH2CH2CH3, CH2CH2CH2CH3, CH2CH2CH2CH3, CH3CH2CH2CH3CH3, the invention discloses a dioxazine compound as well as a synthesis method and application thereof. The dioxazine compound prepared by adopting the method has good solubility, the dispersity of blue pigment is greatly improved, and a pigmentation process is simplified.

Description

Technical Field

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

[0002] There are many varieties of organic pigments, which can be classified into the following main methods: (1) According to the color spectrum of the pigment, it can be divided into red, orange, yellow, green, blue, brown, purple pigments, etc.; (2) According to the chemical structure of the pigment component, it can be divided into azo, phthalocyanine, and heterocyclic pigments; (3) According to its functionality, it can be divided into ordinary and fluorescent organic pigments; (4) According to its use, it can be divided into coating organic pigments, ink organic pigments, cosmetic organic pigments, etc. With the continuous development of organic pigment industry technology, its application field is also expanding, which puts higher requirements on organic pigments.

[0003] Phthalocyanine organic pigments have been widely used as colorants due to their bright colors, high weather resistance and color saturation. However, in the prior art, when the prepared phthalocyanine organic pigments are used, they have poor antioxidant properties and contain metallic copper, which makes the polymer easy to degrade.

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

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

[0006] The product of the present invention 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, rubbers 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, it has a very wide range of applications.

[0007] In a first aspect, the present application provides a dioxazine compound, using the following technical solution:

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

[0009]

[0010] Among them, R1, R2, R3, R4 and R5 are independently selected from H, CH3, C2H5, CH2CH2CH3, CH3CHCH3, CH2CH2CH2CH3, CH3CH2CHCH3, CCH 3CH3CH3, OCH3, OCH2CH3, OCH2CH2CH3, OCHCH3CH3, OCH2CH2CH2CH3, OCH3CHCH2CH3, OCCH3CH3CH3.

[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]

[0015] Among them, R1, R2, R3, R4 and R5 are independently selected from H, CH3, C2H5, CH2CH2CH3, CH3CHCH3, CH2CH2CH2CH3, CH3CH2CHCH3, CCH 3CH3CH3, OCH3, OCH2CH3, OCH2CH2CH3, OCHCH3CH3, OCH2CH2CH2CH3, OCH3CHCH2CH3, OCCH3CH3CH3;

[0016] X is selected from Cl, Br, I.

[0017] Preferably, the specific steps of the synthesis method are as follows:

[0018] (1) dissolving carbazole in a solvent, adding halogenated (alkyl) benzene, and reacting under the action of a phase transfer catalyst to obtain N-(alkyl)phenyl carbazole;

[0019] (2) dissolving N-(alkane)phenylcarbazole in a solvent, adding nitric acid to react, and obtaining 3-nitro-N-(alkane)phenylcarbazole;

[0020] (3) dissolving 3-nitro-N-(alkane)phenylcarbazole in a solvent and reacting with hydrogen under the action of a catalyst to generate 3-amino-N-(alkane)phenylcarbazole;

[0021] (4) Under alkaline conditions, 3-amino-N-(alkyl)phenylcarbazole reacts with tetrachlorobenzoquinone to generate 2,5-dichloro-3,6-di{9-(alkyl)phenyl-3-iminocarbazole}-1,4-benzoquinone, and then a ring-closing agent is added to react to obtain the dioxazine compound shown in Formula 1.

[0022] Preferably, the halogenated (alkyl)benzene in step (1) is chloroalkylbenzene, bromoalkylbenzene or iodoalkylbenzene.

[0023] Preferably, the phase transfer catalyst in step (1) is benzyl-N-triethylammonium chloride.

[0024] Preferably, the reaction temperature in step (1) is 60-150°C.

[0025] Preferably, the solvent used in step (1) is a sodium hydroxide solution with a mass concentration of 40%.

[0026] Preferably, in step (1), the molar ratio of carbazole to halogenated (alkyl) benzene is 1:(1-2); and the phase transfer catalyst is 1-2% of the total mass of carbazole and halogenated (alkyl) benzene.

[0027] Preferably, the reaction temperature in step (2) is 25-100°C.

[0028] Preferably, the solvent used in step (2) is chlorobenzene.

[0029] Preferably, in step (2), the molar ratio of N-(alkane)phenylcarbazole to nitric acid is 1:(1-2).

[0030] Preferably, in step (3), the reaction temperature is 100° C.-150° C., and the reaction pressure is 0.1 MPa-10 MPa.

[0031] Preferably, the solvent used in step (3) is o-dichlorobenzene.

[0032] Preferably, the catalyst in step (3) is an active nickel catalyst.

[0033] Preferably, in step (3), the catalyst is 1-3% of the mass of 3-nitro-N-(alkane)phenylcarbazole; the molar ratio of 3-nitro-N-(alkane)phenylcarbazole to hydrogen is 1:(2-3).

[0034] Preferably, the ring-closing agent in step (4) is benzenesulfonyl chloride; and the base used in step (4) is triethylamine.

[0035] Preferably, the temperature for reacting the ring-closing agent in step (4) is 150-180° C., and the reaction time is 3-10 hours.

[0036] Preferably, the temperature for the reaction of 3-amino-N-(alkane)phenylcarbazole and tetrachlorobenzoquinone in step (4) is 30-100°C.

[0037] Preferably, in step (4), the molar ratio of 3-amino-N-(alkane)phenylcarbazole to tetrachlorobenzoquinone and base is (1.6-1.8):1:(2-2.1).

[0038] Preferably, in step (4), the mass ratio of 2,5-dichloro-3,6-di{9-(alkyl)phenyl-3-iminocarbazole}-1,4-benzoquinone to the ring-closing agent is 2:1.

[0039] In a third aspect, the present application provides an application of a dioxazine compound in a pigment preparation process, using the following technical solution:

[0040] Application of the dioxazine compound or the dioxazine compound prepared by the method in the pigment preparation process.

[0041] In a specific embodiment, a method for synthesizing a dioxazine compound, the synthetic process route is:

[0042] (1) Carbazole is used as the initial raw material, and a halogenated (alkyl) benzene (chloroalkyl benzene, bromoalkyl benzene or iodoalkyl benzene) is added to a sodium hydroxide aqueous solution having a mass concentration of 40%, and the corresponding N-(alkyl) phenyl carbazole is generated under the action of a phase transfer catalyst (benzyl-N-triethylammonium chloride) at 60-150° C., and then pure N-(alkyl) phenyl carbazole is obtained through layer separation.

[0043]

[0044] Among them, R1, R2, R3, R4 and R5 are independently selected from H, CH3, C2H5, CH2CH2CH3, CH3CHCH3, CH2CH2CH2CH3, CH3CH2CHCH3, CCH 3CH3CH3, OCH3, OCH2CH3, OCH2CH2CH3, OCHCH3CH3, OCH2CH2CH2CH3, OCH3CHCH2CH3, OCCH3CH3CH3;

[0045] X is selected from Cl, Br, I.

[0046] (2) N-(Alkyl)phenylcarbazole is reacted with nitric acid having a mass concentration of 50-60% at 25-100° C. in a solvent (chlorobenzene) to generate the corresponding 3-nitro-N-(alkyl)phenylcarbazole, which is then separated to obtain pure 3-nitro-N-(alkyl)phenylcarbazole.

[0047]

[0048] Among them, R1, R2, R3, R4 and R5 are independently selected from H, CH3, C2H5, CH2CH2CH3, CH3CHCH3, CH2CH2CH2CH3, CH3CH2CHCH3, CCH 3CH3CH3, OCH3, OCH2CH3, OCH2CH2CH3, OCHCH3CH3, OCH2CH2CH2CH3, OCH3CHCH2CH3, OCCH3CH3CH3.

[0049] (3) 3-nitro-N-(alkane)phenylcarbazole reacts with hydrogen in a solvent (o-dichlorobenzene) at 100-150° C., 0.1-10 MPa pressure and a catalyst (active nickel catalyst) to generate 3-amino-N-(alkane)phenylcarbazole.

[0050]

[0051] Among them, R1, R2, R3, R4 and R5 are independently selected from H, CH3, C2H5, CH2CH2CH3, CH3CHCH3, CH2CH2CH2CH3, CH3CH2CHCH3, CCH 3CH3CH3, 0CH3, OCH2CH3, OCH2CH2CH3, OCHCH3CH3, OCH2CH2CH2CH3, OCH3CHCH2CH3, OCCH3CH3CH3.

[0052] (4) Under alkaline (triethylamine) conditions at 30-100°C, 3-amino-N-(alkyl)phenylcarbazole reacts with tetrachlorobenzoquinone to generate 2,5-dichloro-3,6-di{9-(alkyl)phenyl-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 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.

[0053]

[0054] Among them, R1, R2, R3, R4 and R5 are independently selected from H, CH3, C2H5, CH2CH2CH3, CH3CHCH3, CH2CH2CH2CH3, CH3CH2CHCH3, CCH 3CH3CH3, OCH3, OCH2CH3, OCH2CH2CH3, OCHCH3CH3, OCH2CH2CH2CH3, OCH3CHCH2CH3, OCCH3CH3CH3.

[0055] In summary, the present application includes at least one of the following beneficial technical effects:

[0056] The present application discloses a dioxazine compound, a synthesis method and an application. 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;

[0057] The dioxazine compound prepared by the method of the present application does not contain metals that have destructive effects on polymer materials and is safe and non-toxic, and has a wide range of applications;

[0058] The preparation method provided in the present application is simple in process, easy to operate and easy to promote. DETAILED DESCRIPTION

[0059] 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.

[0060] The raw materials involved in this application are all commercially available products, and the application is further described in detail below in conjunction with the embodiments and comparative examples.

[0061] The following is a specific embodiment of the method for making the target pigment:

[0062] Example 1: Preparation of N-phenylcarbazole:

[0063] 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 120 g of bromobenzene were added in sequence, the temperature was raised to 120°C with stirring, and the mixture was kept warm and stirred for 3 hours. Samples were taken for liquid chromatography analysis. When the carbazole residue was ≤1‰, the reaction was terminated (if >1‰, the reaction was continued), the unreacted bromobenzene was distilled out, the stirring was stopped, the temperature was kept still and the mixture was separated for 2 hours, and the supernatant (N-phenylcarbazole) was taken out to obtain about 145 g of the product (melting point: about 90°C).

[0064] The specific chemical reaction formula is as follows:

[0065]

[0066] Example 2: Preparation of N-(o-methylphenyl)carbazole

[0067] 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 130 g of o-methylbenzene bromide were added in sequence, the temperature was raised to 120°C with stirring, and the mixture was kept warm and stirred for 3 hours. Samples were taken for liquid chromatography analysis. When the carbazole residue was ≤1‰, the reaction was terminated (if it was >1‰, the reaction was continued), the unreacted o-methylbenzene bromide was distilled out, the stirring was stopped, the temperature was kept still and the layers were separated for 2 hours, and the supernatant N-(o-methylphenyl)carbazole was taken out to obtain about 154 g of the product (melting point: about 95°C).

[0068] The specific chemical reaction formula is as follows:

[0069]

[0070] Example 3: Preparation of N-(2,4-dimethylphenyl)carbazole

[0071] 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 140 g of 2,4-dimethylbenzene bromide were added in sequence, the temperature was raised to 125°C with stirring, the mixture was kept warm and stirred for 3 hours, and a 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 2,4-dimethylbenzene bromide was distilled out, the stirring was stopped, the mixture was kept warm and allowed to stand for 2 hours, and the supernatant N-(2,4-dimethylphenyl)carbazole was taken out to obtain about 163 g of the product (melting point: about 100°C) with a yield of 99.5%.

[0072] The specific chemical reaction formula is as follows:

[0073]

[0074] Example 4: Preparation of 3-nitro-9-phenylcarbazole

[0075] In a 1000 ml three-necked flask equipped with a thermometer and agitator, 100 g of N-phenylcarbazole and 200 g of chlorobenzene, the product of Example 1, were added successively, stirred and warmed to 60 ° C. After N-phenylcarbazole was completely dissolved, 83 g of 50% nitric acid by volume was added dropwise over 120-180 minutes, and the addition was continued to be insulated and stirred for 120 minutes. The mixture was cooled to 0-5 ° C with a salt ice-water bath, stirred at a low speed for 2 hours, and filtered in an insulated state. The three-necked flask material was washed in a filter cake with 50 ml of 0 ° C chlorobenzene, and the filter cake was washed with 500 ml of 30 ° C aqueous solution containing 1% pull-open powder BX by mass concentration, and the filter cake was washed with pure water to pH ≥ 6, the filter cake was removed, and dried at 70 ° C to obtain 101 g of the product with a yield of 85%.

[0076] The specific chemical reaction formula is as follows:

[0077]

[0078] Example 5: Preparation of 3-nitro-9-(o-methyl)phenylcarbazole

[0079] In a 1000 ml three-necked flask equipped with a thermometer and agitator, 100 g of the product N-(o-methylphenyl) carbazole of embodiment 2 and 250 g of chlorobenzene were added successively, stirred and warmed to 65 ℃, after N-(o-methyl)phenyl carbazole was completely dissolved, 85 g of nitric acid with a volume concentration of 50% was added dropwise over 120-180 minutes, and the addition was continued to be insulated and stirred for 120 minutes. Cool to 0-5 ℃ with a salt ice-water bath, stir at a low speed for 2 hours, and filter at a temperature of 50 ml. Wash the three-necked flask material in the filter cake with 50 ml of 0 ℃ of chlorobenzenes, wash the filter cake with 500 ml of 30 ℃ of aqueous solutions containing 1% pull-apart powder BX by mass concentration, wash the filter cake with pure water to pH ≥ 6, remove the filter cake, and dry at 70 ℃ to obtain 101 g of product, with a yield of 86%.

[0080] The specific chemical reaction formula is as follows:

[0081]

[0082] Example 6: Preparation of 3-nitro-9-(2,4-dimethyl)phenylcarbazole

[0083] In a 1000 ml three-necked flask equipped with a thermometer and agitator, 100 g of N-(2,4-dimethylphenyl)carbazole and 300 g of chlorobenzene, the product of Example 3, were added successively, stirred and heated to 65°C, and after N-(2,4-dimethylphenyl)carbazole was completely dissolved, 87 g of 50% nitric acid was added dropwise over 120-180 minutes, and the addition was continued to be insulated and stirred for 120 minutes. Cooled to 0-5°C with a salt ice water bath, insulated and stirred at a low speed for 2 hours, insulated and filtered, the three-necked flask material was washed in a filter cake with 50 ml of 0°C chlorobenzene, the filter cake was washed with 500 ml of a 30°C aqueous solution containing 1% pull-open powder BX by mass concentration, the filter cake was washed with pure water until pH ≥ 6, the filter cake was removed, and dried at 70°C to obtain 100.3 g of the product with a yield of 86%. The specific chemical reaction formula is as follows:

[0084]

[0085] Example 7: Preparation of 3-amino-9-phenylcarbazole

[0086] In a 1000 ml autoclave, 100 g of the product 3-nitro-9-phenylcarbazole of Example 4, 500 g of o-dichlorobenzene, and 2 g of an active nickel catalyst were added in sequence. The autoclave was closed and replaced with vacuum nitrogen 3 times. The temperature was raised to 150° C., and hydrogen was introduced at the same time. The pressure in the autoclave was up to 1.5 MPa, and the entire hydrogenation was controlled according to the reaction rate. After the reaction was completed, the temperature was lowered to 25° C. at room temperature, and the pressure was released to normal pressure. The material was moved into a 1000 ml beaker to separate the catalyst and water. A 3-amino-9-phenylcarbazole o-dichlorobenzene solution was obtained, containing 89.5 g of 3-amino-9-phenylcarbazole.

[0087] The specific chemical reaction formula is as follows:

[0088]

[0089] Example 8: Preparation of 3-amino-9-(o-methyl)phenylcarbazole

[0090] In 1000 ml of autoclave, add 100 g of the product 3-nitro-9-(o-methyl)phenylcarbazole of Example 5, 500 g of o-dichlorobenzene and 2 g of active nickel catalyst successively. Close the autoclave and replace with vacuum nitrogen 3 times. Warm up to 150 ℃, pass hydrogen at the same time, the pressure in the kettle is up to 1.5 MPa, and the whole hydrogenation controls the hydrogen speed according to the reaction speed. After the reaction is finished, cool to 25 ℃ of normal temperatures, release the pressure to normal pressure, move the material into a 1000 ml beaker and separate the catalyst and water. Obtain 3-amino-9-(o-methyl)phenylcarbazole o-dichlorobenzene solution, containing 90.0 g of 3-amino-9-(o-methyl)phenylcarbazole.

[0091] The specific chemical reaction formula is as follows:

[0092]

[0093] Example 9: Preparation of 3-amino-9-(2,4-dimethyl)phenylcarbazole

[0094] In 1000 ml autoclave, add 100 g of the product 3-nitro-9 (2,4-dimethyl) phenylcarbazole of Example 6, 500 g of o-dichlorobenzene and 2 g of active nickel catalyst in sequence. Close the autoclave and replace with vacuum nitrogen 3 times. Warm up to 150 ° C, pass hydrogen at the same time, the pressure in the kettle is up to 1.5 MPa, and the whole hydrogenation controls the hydrogen speed according to the reaction speed. After the reaction is completed, cool to 25 ° C of normal temperature, release the pressure to normal pressure, and move the material into a 1000 ml beaker to separate the catalyst and water. Obtain 3-amino-9-(2,4-dimethyl) phenylcarbazole o-dichlorobenzene solution, containing 90.5 g of 3-amino-9-(2,4-dimethyl) phenylcarbazole.

[0095] The specific chemical reaction formula is as follows:

[0096]

[0097] Example 10: Preparation of Pigment Blue Crude Product 1

[0098] In a 3000 ml three-necked flask equipped with a condenser, a thermometer and a stirrer, the 3-amino-9-phenylcarbazole o-dichlorobenzene solution of Example 7 was added, the volume was adjusted to 2000 ml with o-dichlorobenzene, the temperature was adjusted to 40°C, 40 g of triethylamine was added under stirring, stirring was stopped, 47 g of tetrachlorobenzoquinone was quickly added, and stirring was started to a high speed position for condensation reaction. After 5 minutes, the temperature automatically rose to 65-70°C. If it could not be heated to 70°C, the reaction was stirred for 120 minutes under heat preservation to obtain 100 g of 2,5-dichloro-3,6-bis(9-phenyl-3-iminocarbazole)-1,4-benzoquinone.

[0099] Continue to heat to 140 ° C, add 50 g of benzenesulfonyl chloride, heat to reflux state (175-180 ° C) within 10 minutes, 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 with a yield of 90%.

[0100]

[0101] Example 11: Preparation of Pigment Blue Crude Product 2

[0102] In a 3000 ml three-necked flask equipped with a condenser, a thermometer and a stirrer, the o-dichlorobenzene solution of 3-amino-9-(o-methyl)phenylcarbazole of Example 8 was added, the volume was adjusted to 2000 ml with o-dichlorobenzene, the temperature was adjusted to 40°C, 36 g of triethylamine was added under stirring, stirring was stopped, 48 g of tetrachlorobenzoquinone was quickly added, and stirring was started to a high speed position for condensation reaction. After 5 minutes, the temperature automatically rose to 65-70°C. If it could not be heated to 70°C, the reaction was stirred for 120 minutes under insulation to obtain 90 g of 2,5-dichloro-3,6-di{9-(o-methyl)phenyl-3-iminocarbazole}-1,4-benzoquinone.

[0103] Continue to heat to 140 ° C, add 45 g of benzenesulfonyl chloride, heat to reflux state (175-180 ° C) within 10 minutes, 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 2103.8 g of crude pigment blue with a yield of 88%.

[0104]

[0105] Example 12: Preparation of crude pigment blue 3

[0106] In a 3000 ml three-necked flask equipped with a condenser, a thermometer and a stirrer, the o-dichlorobenzene solution of 3-amino-9-(2,4-dimethyl)phenylcarbazole of Example 9 was added, the volume was adjusted to 2000 ml with o-dichlorobenzene, the temperature was adjusted to 40°C, 35 g of triethylamine was added under stirring, stirring was stopped, 43 g of tetrachlorobenzoquinone was quickly added, and stirring was started to a high speed position for condensation reaction. After 5 minutes, the temperature automatically rose to 65-70°C. If it could not be heated to 70°C, the reaction was stirred for 120 minutes under heat preservation to obtain 88 g of 2,5-dichloro-3,6-di{9-(2,4-dimethyl)phenyl-3-iminocarbazole}-1,4-benzoquinone.

[0107] Continue to heat to 140 ° C, add 44 g of benzenesulfonyl chloride, heat to reflux state (175-180 ° C) within 10 minutes, 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 399.65 g of crude pigment blue with a yield of 85%.

[0108]

[0109] Example 13: Acid-soluble pigmentation

[0110] In a 500 ml three-necked flask equipped with a thermometer and stirrer, add 500 g of 95% concentrated sulfuric acid, slowly add 50 g of the crude product of Example 10 over 50-60 minutes at a temperature of ≤25°C, and stir for 3-5 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.

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

[0112] Example 14: Acid-soluble pigmentation

[0113] In a 500 ml three-necked flask equipped with a thermometer and stirrer, add 500 g of concentrated sulfuric acid with a mass concentration of 95%, slowly add 50 g of the crude product of Example 10 at a temperature of ≤25°C over 50-60 minutes, and stir at this temperature for 3-5 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, and crush to obtain the finished pigment.

[0114] Product features: The crystal particles are slightly coarse and have good covering power.

[0115] Example 15: 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 95% concentrated sulfuric acid, slowly add 25 g of the crude product of Example 10 and 25 g of the crude product of Example 11 over 50-60 minutes at a temperature of ≤25°C, and stir for 3-5 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.

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

[0118] Example 16: Acid-dissolved eutectic crystal method pigmentation

[0119] In a 500 ml three-necked flask equipped with a thermometer and stirrer, add 500 g of 95% concentrated sulfuric acid, slowly add 25 g of the crude product of Example 10 and 25 g of the crude product of Example 12 over 50-60 minutes at a temperature of ≤25°C, and stir for 3-5 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 17: Acid-dissolved eutectic crystal method for pigmentation

[0122] In a 500 ml three-necked flask equipped with a thermometer and stirrer, add 500 g of 95% concentrated sulfuric acid, 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 3-5 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.

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

[0124] Example 18: Pigmentation by Acid-Dissolving Eutectic Crystal Method

[0125] In a 500 ml three-necked flask equipped with a thermometer and stirrer, add 500 g of 95% concentrated sulfuric acid, 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 3-5 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.

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

[0127] Example 19: Kneading method pigmentation

[0128] Into a kneading machine with a capacity of 2000 ml, add 50 g of the crude product of Example 10, 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, stir and beat evenly without lumps, heat to 85°C, keep warm and stir for 120 minutes, cool to 70°C, filter and wash with water until ≥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 20: Kneading method pigmentation

[0131] Into a kneading machine with a capacity of 2000 ml, add 50 g of the crude product of Example 10, 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, stir and beat evenly without lumps, heat to 85°C, keep warm and stir for 120 minutes, cool to 70°C, filter and wash with water until ≥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 21: Pigmentation by kneading eutectic crystal method

[0134] Into a kneading machine with a capacity of 2000 ml, add 45 g of the crude product of Example 10, 5 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, stir and beat evenly without lumps, heat to 85°C, keep warm and stir for 120 minutes, cool to 70°C, filter and wash with water until ≥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 22: Pigmentation by kneading eutectic crystal method

[0137] Into 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 11, 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, stir and beat evenly without lumps, heat to 85°C, keep warm and stir for 120 minutes, cool to 70°C, filter and wash with water until ≥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 23: Pigmentation by kneading eutectic method

[0140] Into a kneading machine with a capacity of 2000 ml, add 45 g of the crude product of Example 10, 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 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, stir and beat evenly without lumps, heat to 85°C, keep warm and stir for 120 minutes, cool to 70°C, filter and wash with water until ≥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 24: Pigmentation by kneading eutectic method

[0143] Into a kneading machine with a capacity of 2000 ml, add 40 g of the crude product of Example 10, 10 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, stir and beat evenly without lumps, heat to 85°C, keep warm and stir for 120 minutes, cool to 70°C, filter and wash with water until ≥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 25: Pigmentation by kneading eutectic method

[0146] Into a kneader with a capacity of 2000 ml, add 40 g of the crude product of Example 10, 5 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, 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 with water until ≥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 26: Pigmentation by kneading eutectic method

[0149] Into a kneader with a capacity of 2000 ml, add 45 g of the crude product of Example 10, 2.5 g of the crude product of Example 11, 2.5 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, stir and beat evenly without lumps, heat to 85°C, keep warm and stir for 120 minutes, cool to 70°C, filter and wash with water until ≥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 27: Pigmentation by ball milling

[0152] In a 3000 ml vertical ball mill, 1000 g of φ6 steel balls, 50 g of the crude product of Example 10, 300 g of anhydrous calcium chloride, and 20 ml of xylene were added in sequence, and circulating water was passed through the jacket. The stirring ball mill was started for 5 hours, and the powder was transferred to a 3000 ml beaker, 2000 ml of water and 200 ml of 30% hydrochloric acid were added, stirred and heated to 85°C, kept warm and stirred for 120 minutes, filtered, washed with water until the pH was ≥6.0 and the chloride ion reached the standard, the filter cake was dried and crushed to obtain the finished pigment.

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

[0154] Example 28: Pigmentation by ball milling

[0155] In 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, and circulating water was passed through the jacket. The stirring ball mill was started for 5 hours, and the powder was transferred to a 3000 ml beaker, 2000 ml of water and 200 ml of 30% hydrochloric acid were added, stirred and heated to 85°C, kept warm and stirred for 120 minutes, filtered, washed with water until the pH was ≥6.0 and the chloride ion reached the standard, the filter cake was dried and crushed to obtain the finished pigment.

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

[0157] Example 29: Pigmentation by eutectic ball milling

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

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

[0160] Example 30: Pigmentation by eutectic ball milling

[0161] In a 3000 ml vertical ball mill, 1000 g of φ6 steel balls, 40 g of the crude product of Example 10, 5 g of the crude product of Example 11, 5 g of the crude product of Example 12, 300 g of anhydrous calcium chloride, and 20 ml of xylene are added in sequence, and circulating water is passed through the jacket. The stirring ball mill is started for 5 hours, and the powder is transferred to a 3000 ml beaker, 2000 ml of water and 200 ml of 30% hydrochloric acid are added, stirred and heated to 85°C, kept warm and stirred for 120 minutes, filtered, washed with water until the pH is ≥6.0 and the chloride ion meets the standard, the filter cake is dried and crushed to obtain a finished pigment.

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

[0163] Application examples:

[0164] Polycarbonate plastic itself is oxidizing, and phthalocyanine pigment used as a colorant will fade during the processing of polycarbonate plastic. The products prepared by using Examples 13 to 30 will not fade when used as a colorant during the processing of polycarbonate plastic.

[0165] Phthalocyanine pigment is used as a colorant for polyethylene plastics. After being placed for half a year, the polyethylene plastic products will be powdered. The products prepared in Examples 13 to 30 are used as colorants to process and 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, R1, R2, R3, R4 and R3 are independently selected from H, CH3, C2H5, CH2CH2CH3, CH3CHCH3, CH2CH2CH2CH3, CH3CH2CHCH3, CCH 3CH3CH3, OCH3, OCH2CH3, OCH2CH2CH3, OCHCH3CH3, OCH2CH2CH2CH3, OCH3CHCH2CH3, OCCH3CH3CH3.

2. A method for synthesizing a dioxazine compound, characterized in that: The synthetic process route of the synthetic method is: Among them, R1, R2, R3, R4 and R5 are independently selected from H, CH3, C2H5, CH2CH2CH3, CH3CHCH3, CH2CH2CH2CH3, CH3CH2CHCH3, CCH 3CH3CH3, OCH3, OCH2CH3, OCH2CH2CH3, OCHCH3CH3, OCH2CH2CH2CH3, OCH3CHCH2CH3, OCCH3CH3CH3; 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 halogenated (alkyl) benzene, and reacting under the action of a phase transfer catalyst to obtain N-(alkyl)phenyl carbazole; (2) dissolving N-(alkane)phenylcarbazole in a solvent, adding nitric acid to react, and obtaining 3-nitro-N-(alkane)phenylcarbazole; (3) dissolving 3-nitro-N-(alkane)phenylcarbazole in a solvent and reacting with hydrogen under the action of a catalyst to generate 3-amino-N-(alkane)phenylcarbazole; (4) Under alkaline conditions, 3-amino-N-(alkyl)phenylcarbazole reacts with tetrachlorobenzoquinone to generate 2,5-dichloro-3,6-di{9-(alkyl)phenyl-3-iminocarbazole}-1,4-benzoquinone, and then a ring-closing agent is added to react to obtain the dioxazine compound shown in Formula 1.

4. The synthesis method according to claim 3, characterized in that: In the step (1), the halogenated (alkyl) benzene is chloroalkyl benzene, bromoalkyl benzene or iodoalkyl benzene; 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 60-150°C; The reaction temperature in step (2) is 25-100° 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 reacting the ring-closing agent in step (4) is 150-180° C., and the reaction time is 3-10 hours. In the step (4), the temperature for the reaction of 3-amino-N-(alkane)phenylcarbazole and tetrachlorobenzoquinone is 30-100°C.

9. The synthesis method according to claim 3, characterized in that: In the step (1), the molar ratio of carbazole to halogenated (alkyl) benzene is 1:(1-2); In the step (1), the phase transfer catalyst is 1-2% of the total mass of carbazole and halogenated (alkyl) benzene; In the step (2), the molar ratio of N-(alkane)phenylcarbazole to nitric acid is 1:(1-2); In the step (3), the catalyst is 1-3% of the mass of 3-nitro-N-(alkane)phenylcarbazole; the molar ratio of 3-nitro-N-(alkane)phenylcarbazole to hydrogen is 1:(2-3); In the step (4), the molar ratio of 3-amino-N-(alkane)phenylcarbazole 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-(alkyl)phenyl-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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