A clean production method for the condensation process of Disperse Blue 60

Abstract

The present invention discloses a clean production method for the condensation process of Disperse Blue 60. Its steps mainly include: feeding materials, stirring, heating up, heating and holding temperature, end point testing, dilution, suction filtration, and washing to obtain the finished product; the condensation process of Disperse Blue 60 adopted by the present invention can improve the stability of the pigment, making it not prone to decomposition and deterioration, and more safe and reliable to use. The pigment after the condensation of Disperse Blue 60 has high color rendering property, with bright and full colors. The properties such as light resistance, heat resistance, and weather resistance of the pigment after the condensation of Disperse Blue 60 have been improved, and its service life is longer.

Description

Technical Field

[0001] The invention relates to the technical field of Disperse Blue No. 60 production, and in particular to a condensation process clean production method of Disperse Blue No. 60. Background Art

[0002] Disperse Blue 60 is a blue synthetic dye, also known as Food Blue 1. It is a water-soluble powder that can be dissolved in water and presents a blue color. Disperse Blue 60 is often used in food, medicine, cosmetics and other fields as a colorant and dye. In the food industry, Disperse Blue 60 is widely used in candy, beverages, chewing gum, ice cream and other products to give the products a beautiful blue color and improve the market competitiveness of the products. In addition, Disperse Blue 60 is also used in medicines as a colorant for capsules, tablets, granules and other preparations.

[0003] In the existing Disperse Blue No. 60 condensation process, dried 1,4-diamino-2,3-dicarboximide anthraquinone and γ-methoxypropylamine are subjected to condensation reaction in anhydrous ethanol medium at reflux temperature. After the reaction is completed, the mixture is filtered to obtain a Disperse Blue No. 60 filter cake. The filtered mother liquor is then distilled to remove ethanol and γ-methoxypropylamine, and the distilled ethanol and γ-methoxypropylamine are reused for the next batch of condensation reactions. In practical applications, the yield of Disperse Blue No. 60 is low, and the condensation product Disperse Blue No. 60 has a certain solubility in ethanol and γ-methoxypropylamine. The distilled ethanol and γ-methoxypropylamine are reused for the next batch of condensation reactions, which directly leads to a low yield of Disperse Blue No. 60. At the same time, the Disperse Blue No. 60 filter cake after filtration contains a certain amount of ethanol and γ-methoxypropylamine, and the consumption of ethanol and γ-methoxypropylamine is also high.

[0004] Chinese patent CN101817989B discloses a method for preparing Disperse Blue 60 and its homologues, wherein "2000 kg of water is placed in a 5000 L enamel kettle, stirring is started, 450 kg of the prepared wet product 1,4-diamino-2,3-dicarboximide anthraquinone is added, after addition, 400 kg of the prepared γ-methoxypropylamine is added, the kettle cover is closed, stirring is performed for half an hour, the temperature is raised to 100° C., the pressure in the kettle is 0.12 MPa, the temperature is kept for 6 hours, and then the temperature is cooled to 60° C., filtered, the mother liquor obtained by filtration is collected in a mother liquor tank, the filter cake is washed with water until it is neutral, and Disperse Blue 60 is obtained". This condensation reaction step requires the addition of a large amount of water, and the reaction needs to be pressurized. The condensation requires relatively strict reaction conditions. Water is used as a solvent, and its consumption is high. The color light DE of the prepared Disperse Blue 60 is greater than 0.5, and the HPLC purity does not meet the requirement of more than 97%.

[0005] It is also reported that a condensation product is obtained by condensation of a mixture of an oxidation anhydride and an imine and γ-methoxypropylamine as raw materials in a mixed solvent of methanol and chlorobenzene, and the target product Disperse Turquoise Blue 60# product is obtained by suction filtration, washing with water and drying. When using solvents such as chlorobenzene, DMF, nitrobenzene, and toluene, impurities such as chlorobenzene in the product cannot meet the relevant requirements of the EU for the total amount of oxygen-containing phenols and the total amount of chlorobenzene and chlorinated methylbenzene.

[0006] Therefore, there is an urgent need for a clean production method for the condensation process of Disperse Blue 60 to solve the above technical problems. Summary of the Invention

[0007] The present invention aims to provide a clean production method for the condensation process of Disperse Blue 60, which can reduce the consumption of ethanol and γ-methoxypropylamine, has simple condensation reaction conditions, clean and environmentally friendly solvents, and a high yield of Disperse Blue 60.

[0008] In order to solve the above technical problems, the present invention adopts the following technical solutions: A clean production method for the condensation process of Disperse Blue 60, comprising the following steps:

[0009] (1) Take an appropriate amount of dry 1,4-diamino-2,3-dicarboximide anthraquinone and put it into a reaction kettle.

[0010] (2) Put an appropriate amount of γ-methoxypropylamine into the above reaction kettle, and then start the stirring device of the reaction kettle to stir.

[0011] (3) Open the reflux pipe valve of the heating device of the reaction kettle to start heating the inside of the reaction kettle.

[0012] (4) After the reaction kettle is heated to the corresponding temperature, keep it warm, and then repeat the heating and insulation operation of the reaction kettle.

[0013] (5) Take an appropriate amount of the sample to be tested from the reaction kettle for end point testing. After the end point testing is qualified, lower the temperature of the reaction kettle to the corresponding temperature.

[0014] (6) Put an appropriate amount of methanol solution into the reaction kettle for dilution, and then continue to cool the reaction kettle.

[0015] (7) Filter the solution in the reaction kettle after cooling in step (6) to obtain the initial solid and the liquid after filtration, and detect the content of γ-methoxypropylamine in the liquid after filtration.

[0016] (8) Put the initial solid into a container, add an appropriate amount of hot water, stir and filter and wash again until the filtrate is clear, and dry the washed wet solid to obtain the finished product of Disperse Blue 60.

[0017] Further, in step (2), the stirring time is 0.5 h.

[0018] Further, in step (4),

[0019] Heat the reaction kettle to 50 °C in 0.7 h and then keep it warm for 0.2 h;

[0020] Continue to heat the reaction kettle to 60 °C in 0.7 h - 0.8 h and keep it warm for 0.2 h;

[0021] Continue to heat the reaction kettle to 70 °C in 0.7 h - 0.8 h and keep it warm for 0.2 h;

[0022] Continue to heat the reaction kettle to 80 °C in 0.7 h - 0.8 h,

[0023] Keep the reaction kettle warm at 80 - 85 °C for 1 h,

[0024] Then continue to heat the reaction kettle to 85 - 95 °C and keep it warm for 1 h.

[0025] Further, in step (5), if the test result does not meet the process numerical requirements, the reaction kettle continues to carry out the heat preservation operation at a certain temperature.

[0026] Further, in step (5), if the test result does not meet the process numerical requirements, add an appropriate amount of γ-methoxypropylamine according to the test situation.

[0027] Further, in step (5), the end point test method is HPLC, and the end point test standard is that the raw material peak is less than 1%.

[0028] Further, in step (5), cool the reaction kettle to 55 - 60 °C in 1 h - 1.2 h.

[0029] Further, in step (6), before adding an appropriate amount of methanol solution, first place the solution in the reaction kettle after cooling for 1.5 - 1.6 h. After adding an appropriate amount of methanol solution, continue to cool the reaction kettle to 35 - 40 °C.

[0030] Further, in step (8), the hot water temperature is 60 - 65 °C.

[0031] The present invention has the following advantages compared with the prior art:

[0032] (1) The condensation process of Disperse Blue 60 adopted by the present invention does not require an absolute ethanol medium. Through continuous operations of heating and heat preservation, and through end point testing, the consumption of ethanol and γ-methoxypropylamine is reduced. At the same time, the reaction conditions do not require a large amount of water consumption, and the condensation reaction can be carried out without pressurization conditions. The solvent is clean and environmentally friendly, and the yield of Disperse Blue 60 is high.

[0033] (2) The condensation process of Disperse Blue 60 adopted in the present invention can improve the stability of the pigment, making it not prone to decomposition and deterioration, and thus safer and more reliable to use. The pigment after the condensation of Disperse Blue 60 has high color rendering property, with bright and full colors. The properties of the pigment after the condensation of Disperse Blue 60, such as light resistance, heat resistance, and weather resistance, have been improved, and it has a longer service life. Description of the Drawings

[0034] Figure 1 It is the process flow chart of the present invention. Detailed Embodiments

[0035] The following is a further description in combination with specific embodiments, but the protection scope of the present invention is not limited thereto.

[0036] The high performance liquid chromatograph (equipped with a diode array detector) used in the embodiment of the present invention is LC-20AT (diode array), and the wavelength range is 190nm - 810nm.

[0037] The color light DE instrument used in the embodiment of the present invention is Konica Minolta CA-310, and the chromaticity range is 0.001 - 160.

[0038] The purity of methanol (CH3OH) used in the embodiment of the present invention is analytical pure.

[0039] Example 1:

[0040] (1) Take 1800 kg of dry 1,4-diamino-2,3-dimethylimide anthraquinone and put it into the reaction kettle.

[0041] (2) Put 2490 kg of γ-methoxypropylamine into the above reaction kettle, then turn on the stirring device of the reaction kettle for stirring, and the stirring time is 0.5 h.

[0042] (3) Open the reflux pipe valve of the temperature rising device in the reaction kettle to start heating the reaction kettle.

[0043] (4) Heat the reaction kettle to 50 °C in 0.7 h and keep it warm for 0.2 h, then continue to heat the reaction kettle to 60 °C in 0.7 h and keep it warm for 0.2 h, continue to heat the reaction kettle to 70 °C in 0.7 h and keep it warm for 0.2 h, continue to heat the reaction kettle to 80 °C in 0.7 h, and then keep the reaction kettle at 80 - 85 °C for 1 h. After this stage of heat preservation ends, continue to heat the reaction kettle to 85 - 95 °C and keep it warm for 1 h.

[0044] (5) Take an appropriate amount of the sample to be tested from the reaction kettle for end - point testing. Use HPLC to measure the peak value of the raw material, that is, measure the peak value of 1,4 - diamino - 2,3 - dimethylimide anthraquinone. If the raw material peak is less than 1%, the test is qualified. After the end - point test is qualified, cool the reaction kettle to 55 - 60 °C within 1h - 1.2h;

[0045] If the measured peak value of the raw material does not meet the process numerical requirements, continue to heat the reaction kettle to 85 - 95 °C and keep it warm for 1h, or add an appropriate amount of fresh γ - methoxypropylamine to the reaction kettle.

[0046] (6) After the end - point test is qualified, add 1580 kg of methanol solution to the reaction kettle for dilution, and then continue to cool the reaction kettle to 35 - 40 °C;

[0047] (7) Filter the solution in the reaction kettle after cooling in step (6) by suction filtration. Filter the mother liquor once to obtain the initial solid and the filtrate after suction filtration, and detect the content of γ - methoxypropylamine in the filtrate after suction filtration;

[0048] (8) Put the initial solid into a container, add hot water at 60 °C, stir and filter - wash again until the filtrate is clear, and dry the wet solid after washing to obtain 1650 kg of finished product of Disperse Blue 60.

[0049] Example 2:

[0050] (1) Take 1800 kg of dry 1,4 - diamino - 2,3 - dimethylimide anthraquinone and put it into the reaction kettle;

[0051] (2) Put 2880 kg of γ - methoxypropylamine into the above - mentioned reaction kettle, then turn on the stirring device of the reaction kettle to stir, and the stirring time is 0.5h;

[0052] (3) Open the reflux pipe valve of the heating device in the reaction kettle to start heating the reaction kettle;

[0053] (4) Heat the reaction kettle to 50 °C in 0.8h and keep it warm for 0.2h, then continue to heat the reaction kettle to 60 °C in 0.8h and keep it warm for 0.2h, continue to heat the reaction kettle to 70 °C in 0.8h and keep it warm for 0.2h, continue to heat the reaction kettle to 80 °C in 0.8h, and then keep the reaction kettle at 80 - 85 °C for 1h. After this section of heat preservation ends, continue to heat the reaction kettle to 85 - 95 °C and keep it warm for 1h.

[0054] (5) Take an appropriate amount of the sample to be tested from the reaction kettle for endpoint testing, and use HPLC to measure the peak value of the raw material, that is, measure the peak value of 1,4-diamino-2,3-diformimidoanthraquinone. If the raw material peak is less than 1%, the test is qualified. After the endpoint test is qualified, cool the reaction kettle to 55-60 °C in 1 h - 1.2 h;

[0055] If the measured peak value of the raw material does not meet the process numerical requirements, continue to heat the reaction kettle to 85-95 °C and keep it warm for 1 h, or add an appropriate amount of fresh γ-methoxypropylamine to the reaction kettle.

[0056] (6) After the endpoint test is qualified, add 1580 kg of methanol solution to the reaction kettle for dilution, and then continue to cool the reaction kettle to 35-40 °C;

[0057] (7) Filter the solution in the reaction kettle after cooling in step (6) by suction filtration, filter the mother liquor once to obtain the initial solid and the liquid after suction filtration, and detect the content of γ-methoxypropylamine in the liquid after suction filtration;

[0058] (8) Put the initial solid into a container, add hot water at 60 °C, stir and filter and wash again until the filtrate is clear, and dry the washed wet solid to obtain the finished product of Disperse Blue 60.

[0059] Example 3:

[0060] (1) Take 1800 kg of dry 1,4-diamino-2,3-diformimidoanthraquinone and put it into the reaction kettle;

[0061] (2) Put 3060 kg of γ-methoxypropylamine into the above reaction kettle, then turn on the stirring device of the reaction kettle to stir, and the stirring time is 0.5 h;

[0062] (3) Open the reflux pipe valve of the temperature-rising device of the reaction kettle to start heating the reaction kettle;

[0063] (4) Heat the reaction kettle to 50 °C in 0.7 h and keep it warm for 0.2 h, then continue to heat the reaction kettle to 60 °C in 0.7 h and keep it warm for 0.2 h, continue to heat the reaction kettle to 70 °C in 0.7 h and keep it warm for 0.2 h, continue to heat the reaction kettle to 80 °C in 0.7 h, and then keep the reaction kettle at 80-85 °C for 1 h. After this period of insulation ends, continue to heat the reaction kettle to 85-95 °C and keep it warm for 1 h.

[0064] (5) Take an appropriate amount of the sample to be tested from the reaction kettle for endpoint testing, and use HPLC to measure the peak value of the raw material, that is, measure the peak value of 1,4-diamino-2,3-diformimidoanthraquinone. If the raw material peak is less than 1%, the test is qualified. After the endpoint test is qualified, cool the reaction kettle to 55-60 °C in 1 h - 1.2 h;

[0065] When the peak value of the raw materials fails to meet the process numerical requirements, continue to heat the reaction kettle to 85 - 95 °C and keep it warm for 1 h, or add an appropriate amount of fresh γ-methoxypropylamine to the reaction kettle.

[0066] (6) After the end-point test is qualified, add 1580 kg of methanol solution to the reaction kettle for dilution, and then continue to cool the reaction kettle to 35 - 40 °C;

[0067] (7) Filter the solution in the reaction kettle after cooling in step (6) by suction filtration, filter the mother liquor once to obtain the initial solid and the liquid after suction filtration, and detect the content of γ-methoxypropylamine in the liquid after suction filtration;

[0068] (8) Put the initial solid into a container, add hot water at 60 °C, stir and filter and wash again until the filtrate is clear, and dry the wet solid after washing to obtain the finished product of Disperse Blue 60.

[0069] It should be noted that the thousand mass ratio of raw material 1,4-diamino-2,3-dicarboximide anthraquinone to γ-methoxypropylamine is 1:1.57 - 1.7.

[0070] It should be noted that the thousand mass ratio of 1,4-diamino-2,3-dicarboximide anthraquinone and diluent methanol in the condensation reaction is 1:0.88.

[0071] It should be noted that the conditions for the condensation reaction are: temperature: 85 - 95 °C.

[0072] It should be noted that in step (7), starting from the third batch, the mother liquor of the previous batch is recycled, and at the same time, fresh γ-methoxypropylamine is added in step (2).

[0073] Perform HPLC determination, color shade DE determination, sample strength determination, and finished product yield statistics on the finished products of Disperse Blue 60 in the above Examples 1, 2, and 3 respectively;

[0074] At the same time, use the preparation methods of Disperse Blue 60 and / or its homologues in Chinese Patent CN103497142B, and the preparation method of a kind of Disperse Blue 60 and its homologues in Chinese Patent CN101817989B to prepare Disperse Blue 60 respectively, and perform HPLC determination, color shade DE determination, sample strength determination, and finished product yield statistics respectively;

[0075] The data are shown in Table 1 below:

[0076] Data comparison in Table 1

[0077]

[0078] It can be clearly seen from the data in Table 1 that the HPLC value, DE value, and sample strength of the finished product of Disperse Blue 60 in Example 1, Example 2, and Example 3 are superior to those in Example 4 and Example 5, and the yield is greater than 91.0%, which is sufficient to prove that the method of the present invention is superior to the existing patented technologies and far exceeds the condensation process methods of Disperse Blue 60 reported in the existing literature.

[0079] Comparison of method conditions:

[0080] 1) The method of the present invention:

[0081] Dry raw material, γ-methoxypropylamine, heating and heat preservation, dilution with methanol, suction filtration and washing

[0082] 2) The method of CN103497142B:

[0083] Wet raw material, a large amount of water, γ-alkoxypropylamine, temperature of 100 °C, vacuum condition, vacuum distillation, filtration and washing

[0084] 3) The method of CN101817989B:

[0085] Wet raw material, a large amount of water, γ-alkoxypropylamine, temperature of 100 °C, pressurized condition, filtration and washing

[0086] On the premise of simplifying the condensation process conditions of Disperse Blue 60, the method of the present invention can also ensure that the HPLC value, DE value, and sample strength of the finished product of Disperse Blue 60 are superior to the existing patented technologies, and the yield of the finished product is greater than 91.0%.

[0087] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail with reference to the embodiments, those of ordinary skill in the art should understand that any modification or equivalent replacement of the technical solutions of the present invention does not depart from the spirit and scope of the technical solutions of the present invention, and they should all be covered by the scope of the claims of the present invention.

Claims

1. A clean production method for the condensation process of Disperse Blue 60, characterized in that: It includes the following steps: (1) Feeding: Take an appropriate amount of dry 1,4-diamino-2,3-dicarboximide anthraquinone and put it into the reaction kettle; (2) Stirring: Put an appropriate amount of γ-methoxypropylamine into the above reaction kettle, and then start the stirring device of the reaction kettle to stir; (3) Heating up: Open the reflux pipe valve of the heating device of the reaction kettle to make the temperature inside the reaction kettle start to rise; (4) Heating up and heat preservation: After the reaction kettle is heated to the corresponding temperature, conduct heat preservation, and then repeat the operation of heating up and heat preservation of the reaction kettle, specifically as follows: Heat the reaction kettle to 50 °C in 0.7 h and then keep it warm for 0.2 h; Continue to heat the reaction kettle to 60 °C in 0.7 h - 0.8 h and keep it warm for 0.2 h; Continue to heat the reaction kettle to 70 °C in 0.7 h - 0.8 h and keep it warm for 0.2 h; Continue to heat the reaction kettle to 80 °C in 0.7 h - 0.8 h; Keep the reaction kettle at a temperature of 80 - 85 °C for 1 h; Then continue to heat the reaction kettle to 85 - 95 °C and keep it warm for 1 h; (5) Endpoint test: Take an appropriate amount of the sample to be tested from the reaction kettle for endpoint test. After the endpoint test is qualified, cool the reaction kettle to 55 - 60 °C in 1 h - 1.2 h; (6) Dilution: Put an appropriate amount of methanol solution into the reaction kettle for dilution, and then continue to cool the reaction kettle to 35 - 40 °C; (7) Vacuum filtration: Filter the solution in the reaction kettle after cooling in step (6) to obtain the initial solid and the liquid after vacuum filtration, and detect the content of γ-methoxypropylamine in the liquid after vacuum filtration; (8) Washing to obtain the finished product: Put the initial solid into a container, add an appropriate amount of hot water, stir and filter and wash again until the filtrate is clear, and dry the wet solid after washing to obtain the finished product of Disperse Blue 60.

2. The clean production method for the condensation process of Disperse Blue 60 according to claim 1, characterized in that: In step (2), the stirring time is 0.5 h.

3. A clean production method for the condensation process of Disperse Blue 60 according to claim 1, characterized in that: In step (5), if the test result does not meet the process numerical requirements, the reaction kettle continues to carry out heat preservation operation at a certain temperature.

4. A clean production method for the condensation process of Disperse Blue 60 according to claim 1, characterized in that: In step (5), if the test result does not meet the process numerical requirements, add an appropriate amount of γ-methoxypropylamine according to the test situation.

5. A clean production method for the condensation process of Disperse Blue 60 according to claim 1, characterized in that: In step (5), the endpoint test method is HPLC, and the endpoint test standard is that the raw material peak is less than 1%.

6. The clean production method for the condensation process of Disperse Blue 60 according to claim 1, characterized in that: In step (8), the hot water temperature is 60 - 65 °C.

Images