CN117024986A - Environment-friendly solvent violet 13 and one-pot production process thereof - Google Patents
Environment-friendly solvent violet 13 and one-pot production process thereof Download PDFInfo
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- LJFWQNJLLOFIJK-UHFFFAOYSA-N solvent violet 13 Chemical compound C1=CC(C)=CC=C1NC1=CC=C(O)C2=C1C(=O)C1=CC=CC=C1C2=O LJFWQNJLLOFIJK-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 35
- 238000005580 one pot reaction Methods 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 88
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 63
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 53
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 claims abstract description 20
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- GUEIZVNYDFNHJU-UHFFFAOYSA-N quinizarin Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(O)=CC=C2O GUEIZVNYDFNHJU-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000007670 refining Methods 0.000 claims abstract description 14
- 238000002425 crystallisation Methods 0.000 claims abstract description 13
- 230000008025 crystallization Effects 0.000 claims abstract description 13
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004327 boric acid Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000009833 condensation Methods 0.000 claims abstract description 10
- 230000005494 condensation Effects 0.000 claims abstract description 10
- 239000004310 lactic acid Substances 0.000 claims abstract description 9
- 235000014655 lactic acid Nutrition 0.000 claims abstract description 9
- 238000004821 distillation Methods 0.000 claims abstract description 8
- 238000010992 reflux Methods 0.000 claims description 26
- 239000000047 product Substances 0.000 claims description 19
- 238000012360 testing method Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- 238000005070 sampling Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 11
- 239000012065 filter cake Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000004128 high performance liquid chromatography Methods 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 239000013014 purified material Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 238000010998 test method Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 9
- 239000002904 solvent Substances 0.000 abstract description 9
- 238000006482 condensation reaction Methods 0.000 abstract description 6
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 6
- 239000006227 byproduct Substances 0.000 abstract description 5
- 239000012535 impurity Substances 0.000 abstract description 5
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 4
- 239000012752 auxiliary agent Substances 0.000 abstract description 3
- 230000002860 competitive effect Effects 0.000 abstract description 3
- 230000007062 hydrolysis Effects 0.000 abstract description 3
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 3
- 238000007086 side reaction Methods 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 2
- 238000004321 preservation Methods 0.000 description 11
- 239000012452 mother liquor Substances 0.000 description 7
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000011343 solid material Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- MCMFEZDRQOJKMN-UHFFFAOYSA-N 1-butylimidazole Chemical compound CCCCN1C=CN=C1 MCMFEZDRQOJKMN-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- ADUMIBSPEHFSLA-UHFFFAOYSA-N 4-[bis(4-aminophenyl)methyl]aniline Chemical compound C1=CC(N)=CC=C1C(C=1C=CC(N)=CC=1)C1=CC=C(N)C=C1 ADUMIBSPEHFSLA-UHFFFAOYSA-N 0.000 description 1
- ZPTVNYMJQHSSEA-UHFFFAOYSA-N 4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1 ZPTVNYMJQHSSEA-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- TVRGPOFMYCMNRB-UHFFFAOYSA-N quinizarine green ss Chemical compound C1=CC(C)=CC=C1NC(C=1C(=O)C2=CC=CC=C2C(=O)C=11)=CC=C1NC1=CC=C(C)C=C1 TVRGPOFMYCMNRB-UHFFFAOYSA-N 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
- C09B1/50—Amino-hydroxy-anthraquinones; Ethers and esters thereof
- C09B1/51—N-substituted amino-hydroxy anthraquinone
- C09B1/514—N-aryl derivatives
- C09B1/5145—N-aryl derivatives only amino and hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
- C07C2603/24—Anthracenes; Hydrogenated anthracenes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The application relates to the technical field of solvent violet 13 production, and in particular discloses an environment-friendly solvent violet 13 and a one-pot production process thereof, wherein methanol, 1, 4-dihydroxyanthraquinone leuco, p-methylaniline, boric acid, lactic acid and DMF are sequentially put into a reaction kettle to be subjected to condensation, distillation crystallization, refining purification and other processes to produce the solvent violet 13. The application avoids the problem of byproduct increase caused by difficult control of hydrogenation reduction, and simultaneously, the addition of solvent DMF and auxiliary agent methanol in the reaction process can lead the condensation reaction process to be single condensation reaction, has high selectivity, avoids the generation of a large amount of impurities due to low selectivity caused by competitive double condensation and hydrolysis side reaction in the prior art, and the production process is finished in a normal pressure reaction kettle without using an autoclave, and has low production danger coefficient; the solvent violet 13 one-pot production process has DE less than 0.5, yield over 93% and less three wastes, and is suitable for large scale production.
Description
Technical Field
The application relates to the technical field of production of solvent violet 13, in particular to environment-friendly solvent violet 13 and a one-pot production process thereof.
Background
Solvent Violet 13 is also called solvent blue 90 and disperse blue 72, its chemical name is 1-hydroxy-4- (p-methylanilino) -anthraquinone, english name is Sovent Violet 13, molecular formula is C 21 H 15 NO 3 The molecular weight is 329.35, and the CAS number is 81-48-1. Its appearanceIs purple black powder, is insoluble in water, is soluble in benzene, chlorobenzene, xylene, DMF and other organic solvents, is dark green in concentrated sulfuric acid, and generates olive-red light blue precipitation after dilution. The solvent violet 13 can be used for coloring various resin plastics, such as polyacrylic resin, ABS resin, polystyrene, organic glass, polyester resin, polycarbonate and the like, so as to obtain red light blue; has excellent heat resistance, sun-proof performance and migration resistance, good tinting strength, high transparency and wide application range.
Currently, the general process for producing solvent violet 13 is: sequentially adding methanol, 1, 4-dihydroxyanthraquinone, paranitrotoluene, iron powder and boric acid into an autoclave, performing nitrogen replacement in a closed container, stirring and heating, performing hydrogenation reduction through hydrogen, performing heat preservation reaction after the reaction system stops absorbing hydrogen, heating after the reaction is finished, performing condensation reaction, cooling after the reaction is finished, decompressing, introducing air for oxidation reaction, finally adding hydrochloric acid for pulping, filtering, washing and drying to obtain the solvent violet 13. The quality of the solvent violet 13 product is difficult to control by adopting hydrogenation, the byproduct C.I. solvent green 3 is more generated, the color light reproducibility is poor, the hue DE is more than 0.5, and the color light is greenish.
In addition, researches and records that the process adopting N-butanol as a condensation solvent and the condensation process of N-butylimidazole, an auxiliary agent, chloroethane and the like are carried out in an autoclave, the process is difficult to realize large-scale production, the solvent waste in the process is serious, and the environment is polluted; and the product contains impurities such as chlorobenzene, chlorophenol and the like. The competitive double condensation and hydrolysis side reactions generated in the reaction process are not easy to control, and the reaction selectivity is affected, so that the yield of the finished product is low.
In addition, 1, 4-dihydroxyanthraquinone leuco and p-methylaniline are used as raw materials, water is used as a reaction medium to carry out condensation reaction in an autoclave in the presence of alkali, boric acid and a phase transfer catalyst, and after the reaction is finished, the materials are filtered, washed and dried to obtain a solvent purple 13 product.
Meanwhile, the production processes in the prior art can be completed in an autoclave, so that the production risk coefficient is high, and the large-scale production difficulty is high. Therefore, research and development of an environment-friendly solvent violet 13 and a one-pot production process thereof are needed to solve the technical problems in the process.
Disclosure of Invention
Aiming at the technical problems, the application provides the environment-friendly solvent purple 13 with few byproducts and impurities, high yield and low production risk coefficient and the production process thereof, and solves the problems of more byproducts and impurities, low yield, high production risk coefficient, large difficulty in realizing large-scale production and the like in the existing production process.
In order to solve the technical problems, the environment-friendly solvent purple 13 is prepared by mixing 1, 4-dihydroxyanthraquinone, methanol, 1, 4-dihydroxyanthraquinone leuco, p-methylaniline, boric acid, lactic acid and DMF according to the mass ratio of 1:0.3 to 0.5:0.1 to 0.2:0.45 to 0.55:0.1 to 0.2:0.01 to 0.05:1.5 to 2.5.
The application also discloses an environment-friendly solvent violet 13 one-pot production process, which specifically comprises the following steps:
s1, feeding: sequentially adding methanol, 1, 4-dihydroxyanthraquinone leuco, p-methylaniline, boric acid, lactic acid and DMF into a reaction kettle;
s2, nitrogen substitution: after the reaction kettle is closed, nitrogen replacement is carried out on the reaction kettle;
s3, condensation reflux: starting the reaction kettle to stir the materials, heating the materials to a reflux pipe of the reaction kettle to start reflux, and controlling the temperature to maintain reflux reaction for a period of time;
s4 reaction endpoint test: sampling to detect a reaction end point when the temperature is reduced to no reflux;
s5, distilling and crystallizing: after detecting that the reaction end point is qualified, heating and distilling the reaction kettle, preserving heat for a period of time after finishing the distillation, naturally cooling, sampling and observing the crystallization condition;
s6, refining and purifying: cooling after crystallization is qualified, and adding a certain amount of DMF and methanol into a reaction kettle for refining and purifying;
s7, filtering: putting the refined and purified material into a membrane filter press for filtering to obtain a filter cake;
s8, washing and drying: and adding hot water into the filter cake for washing, and drying the fixed material after washing to obtain a solvent violet 13 finished product.
In S3, the temperature of the condensation reflux reaction is controlled to be 95-107 ℃, and the reflux reaction time is maintained to be not less than 8 hours.
In S4, the reaction end point test method is HPLC, and the end point test standard is that the raw material peak is less than 1%.
And S4, if the reaction end point test is not qualified, continuously controlling the temperature for not less than 2 hours, and repeatedly testing the reaction end point until the reaction end point test is qualified.
In S5, the distillation temperature is controlled to be 118-125 ℃, the distillation time is 2.5 hours, and the heat preservation is carried out for 0.5-1 hour after the distillation is finished.
In S6, cooling to 50-65 ℃ after crystallization is qualified.
Further, in S6, the mass ratio of the total mass of DMF and methanol to the mass of the crystal in S5 is 2 to 3:1, wherein the mass ratio of DMF to methanol is 1:3.
further, after S7 filtration, the mother liquor is recovered to a rectifying still, and is used for the next batch of materials after rectification and purification.
In S8, the temperature of the hot water for washing is 80 to 85 ℃.
Compared with the prior art, the application has the following advantages:
the solvent purple 13 one-pot production process of the application avoids the problem of byproduct increase caused by difficult control of hydrogenation reduction, and simultaneously, the addition of solvent DMF and auxiliary agent methanol can lead the condensation reaction process to be single condensation reaction in the reaction process, has high selectivity, avoids a large amount of impurities generated by low selectivity caused by competitive double condensation and hydrolysis side reaction in the prior art, and the production process is completed in an atmospheric pressure reaction kettle without using an autoclave, and has low production risk coefficient; the solvent violet 13 one-pot production process has DE less than 0.5, yield over 93%, less water consumption, less three wastes and suitable for large scale production.
Drawings
FIG. 1 is a process flow diagram of the present application.
Detailed Description
The application is further illustrated below with reference to examples.
Example 1:
adding 2500kg of DMF, 670kg of p-methylaniline, 55kg of lactic acid, 130kg of 1, 4-dihydroxyanthraquinone leuco, 135kg of boric acid and 480kg of methanol into a reaction kettle through a DMF metering tank or a recovery storage tank, closing a feed valve after feeding, sealing the reaction kettle, replacing the reaction kettle for 3 minutes by using nitrogen, and then starting the reaction kettle for stirring; after confirming that the temperature is correct, the temperature is raised for 1.3 hours until the reflux starts, and the reflux reaction is maintained at 95 ℃ for 8 hours.
And after the reflux heat preservation is finished, naturally cooling the reaction kettle, opening a sampling valve to sample when the temperature is reduced to be free of reflux, measuring the raw material peak value of the sample by using HPLC, and judging the reaction end point, wherein the 1, 4-dihydroxyanthraquinone peak value is qualified when the peak value is less than 1%. If the reaction end point test is not qualified, continuing to control the temperature for not less than 2 hours, and retesting the reaction end point until the end point is reached.
After the reaction end point test is qualified, heating and distilling the reaction kettle, controlling the distilling temperature to be 118 ℃, keeping the heat preservation for 0.5 hour after the distilling is finished, stopping heat preservation, naturally cooling to a reflux-free state, and sampling and observing the crystallization condition; after the crystallization is observed to be qualified, circulating water is started to cool the reaction kettle, the reaction kettle is cooled to 50 ℃, and the circulating water is closed, and the time is 1.5 hours.
Adding 800kg of DMF and 2400kg of methanol into a reaction kettle for refining and purifying, wherein the refining temperature is controlled at 50 ℃ and the refining time is 2 hours; introducing the refined material into a membrane filter press, recovering mother liquor to a rectifying kettle, collecting the mother liquor for the next batch of material after rectifying and purifying, adding 4500kg of hot water with the temperature of 85 ℃ into the obtained filter cake for washing, washing the filter cake to be neutral and clear, and drying the obtained solid material.
1600kg of solvent violet 13 product is obtained after drying, and the yield of the finished product reaches 93.7%. The solvent violet 13 product is detected by sampling, the purity is 98.1%, the DE value is 0.46, and the color light is blue.
Example 2:
adding 3250kg of DMF, 715kg of p-methylaniline, 65kg of lactic acid, 260kg of 1, 4-dihydroxyanthraquinone leuco, 260kg of boric acid and 650kg of methanol into a reaction kettle through a DMF metering tank or a recovery storage tank, closing a charging valve after the material is completely charged, sealing the reaction kettle, replacing the reaction kettle for 3 minutes by using nitrogen, and then starting the reaction kettle for stirring; after confirming that the temperature was not wrong, the temperature was raised for 1.5 hours until the reflux was started, and the reflux reaction was maintained at 107℃for 8.2 hours.
And after the reflux heat preservation is finished, naturally cooling the reaction kettle, opening a sampling valve to sample when the temperature is reduced to be free of reflux, measuring the raw material peak value of the sample by using HPLC, and judging the reaction end point, wherein the 1, 4-dihydroxyanthraquinone peak value is qualified when the peak value is less than 1%. If the reaction end point test is not qualified, continuing to control the temperature for not less than 2 hours, and retesting the reaction end point until the end point is reached.
After the reaction end point test is qualified, heating and distilling the reaction kettle, controlling the distilling temperature to be 125 ℃, keeping the heat preservation for 0.8 hour after the distilling is finished, stopping heat preservation, naturally cooling to a reflux-free state, and sampling and observing the crystallization condition; after the crystallization is observed to be qualified, circulating water is started to cool the reaction kettle, the reaction kettle is cooled to 65 ℃, and the circulating water is closed, and the time is 1.4 hours.
Adding 1240kg of DMF and 3720kg of methanol into a reaction kettle for refining and purifying, wherein the refining temperature is controlled at 60 ℃ and the refining time is 2 hours; introducing the refined material into a membrane filter press, recovering mother liquor to a rectifying kettle, collecting the mother liquor for the next batch of material after rectifying and purifying, adding the obtained filter cake into hot water with the weight of 5500kg at the temperature of 85 ℃ for washing, washing the filter cake to be neutral and clear, and drying the obtained solid material.
After drying, 1590kg of solvent violet 13 product is obtained, and the yield of the finished product reaches 93.3%. And (3) detecting the solvent violet 13 product by sampling, wherein the purity is 98.6%, the DE value is 0.12, and the chromatic light is bluish.
Example 3:
adding 2600kg of DMF, 650kg of p-methylaniline, 40kg of lactic acid, 200kg of 1, 4-dihydroxyanthraquinone leuco, 200kg of boric acid and 520kg of methanol into a reaction kettle through a DMF metering tank or a recovery storage tank, closing a feed valve after feeding, sealing the reaction kettle, replacing the reaction kettle for 3 minutes by using nitrogen, and then starting the reaction kettle for stirring; after confirming that the temperature is correct, the temperature is raised for 1 hour until the reflux starts, and the reflux reaction is maintained at 100 ℃ for 8.4 hours.
And after the reflux heat preservation is finished, naturally cooling the reaction kettle, opening a sampling valve to sample when the temperature is reduced to be free of reflux, measuring the raw material peak value of the sample by using HPLC, and judging the reaction end point, wherein the 1, 4-dihydroxyanthraquinone peak value is qualified when the peak value is less than 1%. If the reaction end point test is not qualified, continuing to control the temperature for not less than 2 hours, and retesting the reaction end point until the end point is reached.
Heating and distilling the reaction kettle after the reaction end point test is qualified, controlling the distilling temperature to reach 120 ℃, keeping the heat preservation for 1 hour after the distilling is finished, stopping heat preservation, naturally cooling to a reflux-free state, and sampling and observing the crystallization condition; after the crystallization is observed to be qualified, circulating water is started to cool the reaction kettle, the reaction kettle is cooled to 58 ℃, and the circulating water is closed, and the time is 1.5 hours.
Adding 1030kg of DMF and 3090kg of methanol into a reaction kettle for refining and purifying, wherein the refining temperature is controlled at 55 ℃ and the refining time is 2 hours; introducing the refined material into a membrane filter press, recovering mother liquor to a rectifying kettle, collecting the mother liquor for the next batch of material after rectifying and purifying, adding hot water with the weight of 4700kg at 80 ℃ into the obtained filter cake for washing, washing the filter cake to be neutral and clear, and drying the obtained solid material.
1650kg of solvent violet 13 product is obtained after drying, and the yield of the product reaches 93.9%. And (3) detecting the solvent violet 13 product by sampling, wherein the purity is 98.2%, the DE value is 0.35, and the chromatic light is bluish.
It should be noted that:
in examples 1-3 above, the high performance liquid chromatograph (diode array detector) used for the detection was LC-20AT (diode array), wavelength range: 190nm-810nm.
The color DE instrument for detecting the used color light is Konica Minolta CA-310, and the chromaticity range is 0.001-160.
The production process devices described in the above embodiments are all known in the art, and the specific structure and the usage manner thereof will not be described in detail in this embodiment.
The DMF described in the above examples is N, N-dimethylformamide, and methanol, 1, 4-dihydroxyanthraquinone leuco, p-methylaniline, boric acid, lactic acid and DMF are all commercially available raw materials which can be directly purchased.
The solvent violet 13 products obtained in examples 1-3 above, and the solvent violet 13 products produced by the three prior art production processes described in the background art were each measured and compared as shown in table 1 below:
TABLE 1 comparison of solvent Violet 13 data
From the data in Table 1, it can be seen that the purity, DE value and other data of the solvent violet 13 product obtained in examples 1-3 of the application are all superior to those of the solvent violet 13 produced in the prior art, and the yield of the finished product is more than 93%; meanwhile, the reaction in the embodiments 1-3 can be carried out by using an atmospheric pressure reaction kettle, compared with the three production processes disclosed in the prior art, which all use an autoclave for production, the production safety factor is greatly improved, and the method is more suitable for large-scale production; therefore, compared with the prior art, the solvent violet 13 one-pot production process disclosed by the application is obviously improved.
Claims (9)
1. An environment-friendly solvent violet 13, which is characterized in that: 1, 4-dihydroxyanthraquinone, methanol, 1, 4-dihydroxyanthraquinone leuco, p-methylaniline, boric acid, lactic acid and DMF are mixed according to the mass ratio of 1:0.3 to 0.5:0.1 to 0.2:0.45 to 0.55:0.1 to 0.2:0.01 to 0.05:1.5 to 2.5.
2. An environment-friendly solvent violet 13 one-pot production process is characterized in that: the method comprises the following steps:
s1, feeding: sequentially adding methanol, 1, 4-dihydroxyanthraquinone leuco, p-methylaniline, boric acid, lactic acid and DMF into a reaction kettle;
s2, nitrogen substitution: after the reaction kettle is closed, nitrogen replacement is carried out on the reaction kettle;
s3, condensation reflux: starting the reaction kettle to stir the materials, heating the materials to a reflux pipe of the reaction kettle to start reflux, and controlling the temperature to maintain reflux reaction for a period of time;
s4 reaction endpoint test: sampling to detect a reaction end point when the temperature is reduced to no reflux;
s5, distilling and crystallizing: after detecting that the reaction end point is qualified, heating and distilling the reaction kettle, preserving heat for a period of time after finishing the distillation, naturally cooling, sampling and observing the crystallization condition;
s6, refining and purifying: cooling after crystallization is qualified, and adding a certain amount of DMF and methanol into a reaction kettle for refining and purifying;
s7, filtering: putting the refined and purified material into a membrane filter press for filtering to obtain a filter cake;
s8, washing and drying: and adding hot water into the filter cake for washing, and drying the fixed material after washing to obtain a solvent violet 13 finished product.
3. The environment-friendly solvent violet 13 one-pot production process of claim 2, characterized in that: and S3, controlling the temperature of the condensation reflux reaction at 95-107 ℃ and maintaining the reflux reaction time to be not less than 8 hours.
4. The environment-friendly solvent violet 13 one-pot production process of claim 2, characterized in that: in S4, the reaction endpoint test method is HPLC, and the endpoint test standard is that the raw material peak is less than 1%.
5. The environment-friendly solvent violet 13 one-pot production process of claim 2, characterized in that: and S4, if the reaction end point test is not qualified, continuously controlling the temperature for at least 2 hours, and then repeatedly testing the reaction end point until the reaction end point test is qualified.
6. The environment-friendly solvent violet 13 one-pot production process of claim 2, characterized in that: s5, controlling the distillation temperature at 118-125 ℃, distilling for 2.5 hours, and preserving heat for 0.5-1 hour after the distillation is finished.
7. The environment-friendly solvent violet 13 one-pot production process of claim 2, characterized in that: and S6, cooling to 50-65 ℃ after crystallization is qualified.
8. The environment-friendly solvent violet 13 one-pot production process of claim 2, characterized in that: in S6, the mass ratio of the total mass of DMF and methanol to the mass of the crystal in S5 is 2-3: 1, wherein the mass ratio of DMF to methanol is 1:3.
9. the environment-friendly solvent violet 13 one-pot production process of claim 2, characterized in that: in S8, the temperature of the hot water for washing is 80-85 ℃.
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