CN114573998B - Pigment yellow 139 synthesis process - Google Patents
Pigment yellow 139 synthesis process Download PDFInfo
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- CN114573998B CN114573998B CN202210105657.9A CN202210105657A CN114573998B CN 114573998 B CN114573998 B CN 114573998B CN 202210105657 A CN202210105657 A CN 202210105657A CN 114573998 B CN114573998 B CN 114573998B
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- pigment yellow
- diiminoisoindoline
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- 239000000049 pigment Substances 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 48
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 11
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 11
- RZVCEPSDYHAHLX-UHFFFAOYSA-N 3-iminoisoindol-1-amine Chemical compound C1=CC=C2C(N)=NC(=N)C2=C1 RZVCEPSDYHAHLX-UHFFFAOYSA-N 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000001914 filtration Methods 0.000 claims abstract description 25
- HNYOPLTXPVRDBG-UHFFFAOYSA-N barbituric acid Chemical compound O=C1CC(=O)NC(=O)N1 HNYOPLTXPVRDBG-UHFFFAOYSA-N 0.000 claims abstract description 23
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000004202 carbamide Substances 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims abstract description 20
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000002844 melting Methods 0.000 claims abstract description 13
- 230000008018 melting Effects 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000007670 refining Methods 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 60
- 238000010438 heat treatment Methods 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 16
- 150000003863 ammonium salts Chemical class 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- 239000012065 filter cake Substances 0.000 claims description 10
- 230000002194 synthesizing effect Effects 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 9
- 238000009833 condensation Methods 0.000 claims description 9
- 230000005494 condensation Effects 0.000 claims description 9
- 239000005711 Benzoic acid Substances 0.000 claims description 8
- 235000010233 benzoic acid Nutrition 0.000 claims description 8
- 239000000853 adhesive Substances 0.000 claims description 6
- 230000001070 adhesive effect Effects 0.000 claims description 6
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 6
- 239000011609 ammonium molybdate Substances 0.000 claims description 6
- 229940010552 ammonium molybdate Drugs 0.000 claims description 6
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 4
- 238000004537 pulping Methods 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 abstract description 32
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 abstract description 11
- 229920006391 phthalonitrile polymer Polymers 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 230000018044 dehydration Effects 0.000 abstract description 6
- 238000006297 dehydration reaction Methods 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 4
- 238000010309 melting process Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 26
- 238000002360 preparation method Methods 0.000 description 11
- 239000002253 acid Substances 0.000 description 9
- 239000002351 wastewater Substances 0.000 description 7
- 239000012535 impurity Substances 0.000 description 6
- 239000012043 crude product Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 239000007853 buffer solution Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 3
- 235000019796 monopotassium phosphate Nutrition 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007656 barbituric acids Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- GWVMLCQWXVFZCN-UHFFFAOYSA-N isoindoline Chemical compound C1=CC=C2CNCC2=C1 GWVMLCQWXVFZCN-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 230000019612 pigmentation Effects 0.000 description 1
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002699 waste material 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
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/04—Isoindoline dyes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a pigment yellow 139 synthesis process, which belongs to the technical field of pigment production and comprises the following steps: the solid state melting process is adopted to synthesize 1, 3-diiminoisoindoline by phthalic anhydride and urea in a batch mode or a continuous mode or a combination mode of batch and continuous modes, and the 1, 3-diiminoisoindoline reacts with barbituric acid to synthesize crude pigment yellow 139 under the action of a catalyst. The beneficial effects of the invention are as follows: the solid state melting method uses phthalic anhydride and urea, so that the problem of phthalonitrile is avoided, and the large-scale production of pigment yellow 139 is facilitated; the dehydration and drying process of the refining process of the 1, 3-diiminoisoindoline is omitted, the process time is shortened, and a large amount of energy consumption is saved; by adopting the high-temperature filtering method, the cyanuric acid content can be maintained below 30ppm, the loss of pigment yellow 139 along with a large amount of hot water can be avoided, and the yield of pigment yellow 139 is ensured.
Description
Technical field:
the invention belongs to the technical field of pigment production, and particularly relates to a pigment yellow 139 synthesis process.
The background technology is as follows:
pigment yellow 139 is one of isoindoline pigments, and has a more planar molecular structure because it contains carbonyl, imino, cyano, amide, and the like in its molecule, thereby forming intramolecular and intermolecular hydrogen bonds. Pigment yellow 139 is therefore an organic pigment having excellent heat resistance and solvent resistance.
The preparation method of pigment yellow 139 mainly comprises the following steps: in the presence of alkali, phthalonitrile reacts in alcohol, and then the obtained intermediate reacts with barbituric acid compounds to obtain the target product.
The national invention patent as patent No. 201110447652.6 discloses a process for preparing c.i. pigment yellow 139. The method comprises
(1) A step of preparing 1, 3-diiminoisoindoline from phthalonitrile;
(2) A step of preparing crude pigment yellow 139 from 1, 3-diiminoisoindoline and barbituric acid;
(3) A step of pigmentation of crude pigment yellow 139;
the invention not only improves the yield of the C.I. pigment yellow 139, but also the obtained pigment has excellent properties such as high tinting strength, bright color, good dispersion performance, excellent light fastness, weather fastness and the like.
However, the production process route of the phthalonitrile in China is complex, the production cost is high, and the pollution is relatively large, so that manufacturers are relatively few, the pollution is greatly influenced by environmental protection and safety in recent years, and the product supply is seriously insufficient.
The invention comprises the following steps:
in order to solve the problems and overcome the defects in the prior art, the invention provides a pigment yellow 139 synthesis process which can effectively solve the problem that the production of pigment yellow 139 prepared from phthalonitrile is limited due to the serious deficiency of phthalonitrile supply.
The specific technical scheme for solving the technical problems is as follows: the synthesis process of pigment yellow 139 is characterized by comprising the following steps:
(1) Synthesizing 1, 3-diiminoisoindoline by using phthalic anhydride and urea in a solid state melting method in a batch mode or a continuous mode or a combination mode of batch mode and continuous mode under the action of a catalyst,
(2) Crude pigment yellow 139 was synthesized from 1, 3-diiminoisoindoline and barbituric acid.
Further, the step (1): adding urea and ammonium salt into a reactor, heating to melt, adding a catalyst, dehydrating at 120-135 ℃ for 2-3 hours, adding phthalic anhydride after dehydration, imidizing at 130-150 ℃ for 3 hours, continuously heating to 160-180 ℃ and preserving heat for 5-7 hours for condensation, cooling to below 60 ℃ after condensation is completed, adding water, stirring, adding sodium hydroxide, dissolving, precipitating, spin-drying and drying materials to obtain the 1, 3-diiminoisoindoline.
Further, the step (1): adding urea and ammonium salt into a reactor, heating to melt, adding a catalyst, dehydrating at 120-135 ℃ for 2-3 hours, slowly adding phthalic anhydride into the reactor after dehydrating, imidizing at 130-150 ℃ for 3 hours, continuously heating to 160-180 ℃ for 5-7 hours for condensation, vacuumizing after the condensation is finished, and cooling to below 60 ℃ to obtain the adhesive melt of the 1, 3-diiminoisoindoline.
Further, the step (2): adding alcohol and alkali into 1, 3-diiminoisoindoline, stirring and dissolving to be transparent, adding barbituric acid, heating and refluxing for reaction for 3 hours, adding sulfuric acid, adding benzoic acid, continuously heating and refluxing for reaction for 3-8 hours, distilling out methanol, press filtering and filtering, washing a filter cake until the filter cake is neutral to obtain pigment yellow 139,
the catalyst in the step (1) is ammonium molybdate, the alcohol in the step (2) is methanol, and the alkali is sodium hydroxide.
Further, in the step (1), the mass parts ratio of urea, ammonium salt, ammonium molybdate and phthalic anhydride is as follows: (2-3): (1.5-2.5): (0.01-0.02): 1.
further, in the step (2), the mass part ratio of the 1, 3-diiminoisoindoline, the methanol, the sodium hydroxide, the barbituric acid, the sulfuric acid and the benzoic acid is as follows: 2.5: (65-75): (0.2-0.6): (1-1.5): (0.2-0.3): (0.1-0.3).
Further, the method also comprises a refining procedure of crude pigment yellow 139: adding water into a reaction kettle, adding crude pigment yellow 139, pulping uniformly, heating to 150 ℃, treating for 5-10 hours under the pressure of 0.45MPa, cooling to 70 ℃, filtering, washing, drying and crushing to obtain a pigment yellow 139 product.
Further, the mass ratio of the crude pigment yellow 139 to water is 1:4.
The beneficial effects of the invention are as follows:
the invention creatively utilizes a solid-state melting method to synthesize the 1, 3-diiminoisoindoline by phthalic anhydride and urea under the action of the catalyst, avoids the problem of phthalonitrile, and is beneficial to the large-scale production of pigment yellow 139;
the molten 1, 3-diiminoisoindoline is adopted for direct reaction, so that the dehydration and drying process in the refining process of the 1, 3-diiminoisoindoline is omitted, the process time is shortened, and a large amount of energy consumption is saved;
the reaction system is methanol, a large amount of anhydrous solvent is added, and the residual acid wastewater is little along with the distillation of the methanol, so that the generation of a large amount of acid wastewater is avoided;
by adopting the high-temperature filtering method, the cyanuric acid content can be maintained below 30ppm, the loss of pigment yellow 139 along with a large amount of hot water can be avoided, and the yield of pigment yellow 139 is ensured.
The specific embodiment is as follows:
specific details are set forth in the description of the invention in order to provide a thorough understanding of embodiments of the invention, it will be apparent to those skilled in the art that the invention is not limited to these details. In other instances, well-known structures and functions have not been shown or described in detail to avoid obscuring aspects of embodiments of the invention. The specific meaning of the above terms in the present invention will be understood in specific cases by those of ordinary skill in the art.
Specific embodiments of the invention:
example 1:
the synthesis process of pigment yellow 139 comprises the following steps:
(1) Synthesizing 1, 3-diiminoisoindoline by using phthalic anhydride and urea in a solid state melting method in a batch mode or a continuous mode or a combination mode of batch mode and continuous mode under the action of a catalyst,
(2) Crude pigment yellow 139 was synthesized from 1, 3-diiminoisoindoline and barbituric acid.
The step (1) is specifically as follows:
adding urea and ammonium salt into a reactor, heating to melt, adding a catalyst, dehydrating for 2-3 hours at 120-135 ℃, adding phthalic anhydride after dehydration, carrying out imidization reaction for 3 hours at 130-150 ℃, continuously heating to 160-180 ℃, preserving heat for 5-7 hours, condensing, cooling to below 60 ℃ after condensation is finished, adding water, stirring, adding sodium hydroxide, dissolving, precipitating, spin-drying and drying materials to obtain 1, 3-diiminoisoindoline, wherein the catalyst is ammonium molybdate, urea, ammonium salt, catalyst and phthalic anhydride, and the mass portion ratio of the catalyst to the phthalic anhydride is as follows: (2-3): (1.5-2.5): (0.01-0.02): 1.
the ammonium salt may be an inorganic ammonium salt of ammonium nitrate or ammonium chloride, or an organic ammonium salt.
The step (2) is specifically as follows:
adding alcohol and alkali into 1, 3-diiminoisoindoline, stirring and dissolving to be transparent, adding barbituric acid, heating and refluxing for reaction for 3 hours, adding sulfuric acid, adding benzoic acid, continuously heating and refluxing for reaction for 3-8 hours, distilling out methanol, press filtering and filtering, washing a filter cake until the filter cake is neutral to obtain pigment yellow 139,
the weight part ratio of the 1, 3-diiminoisoindoline, methanol, alkali, barbituric acid, sulfuric acid and benzoic acid is as follows: 2.5: (65-75): (0.2-0.6): (1-1.5): (0.2-0.6): (0.1-0.3).
Further, the refining procedure of crude pigment yellow 139 is included: adding water into a reaction kettle, adding crude pigment yellow 139, pulping uniformly, heating to 150 ℃, treating for 5-10 hours under the pressure of 0.45MPa, cooling to 70 ℃, filtering, washing, drying and crushing to obtain a pigment yellow 139 product.
Further, the mass part ratio of the crude pigment yellow 139 to water is 1 (4-6).
Example 2
The synthesis process of pigment yellow 139 comprises the following steps:
(1) Synthesizing 1, 3-diiminoisoindoline by using phthalic anhydride and urea in a solid state melting method in a batch mode or a continuous mode or a combination mode of batch mode and continuous mode under the action of a catalyst,
(2) Crude pigment yellow 139 was synthesized from 1, 3-diiminoisoindoline and barbituric acid.
The step (1) is specifically as follows:
adding urea and ammonium salt into a reactor, heating to melt, adding a catalyst, dehydrating at 120-135 ℃ for 2-3 hours, slowly adding phthalic anhydride into the reactor after dehydrating, imidizing at 130-150 ℃ for 3 hours, continuously heating to 160-180 ℃ for 5-7 hours for condensation, vacuumizing after the condensation is completed, and cooling to below 60 ℃ to obtain the 1, 3-diiminoisoindoline adhesive melt. The catalyst is ammonium molybdate, urea, ammonium salt, ammonium molybdate and phthalic anhydride in parts by weight: (2-3): (1.5-2.5): (0.01-0.02): 1.
the ammonium salt may be an inorganic ammonium salt of ammonium nitrate or ammonium chloride, or an organic ammonium salt.
The step (2) is specifically as follows:
adding alcohol and alkali into the 1, 3-diiminoisoindoline adhesive melt, stirring and dissolving until the mixture is transparent, adding barbituric acid, heating and refluxing for reaction for 3 hours, adding sulfuric acid, adding benzoic acid, continuously heating and refluxing for reaction for 3-8 hours, distilling methanol, press-filtering and filtering, washing a filter cake until the filter cake is neutral to obtain pigment yellow 139,
the weight part ratio of the 1, 3-diiminoisoindoline, methanol, alkali, barbituric acid, sulfuric acid and benzoic acid is as follows: 2.5: (65-75): (0.2-0.6): (1-1.5): (0.2-0.6): (0.1-0.3).
Further, the refining procedure of crude pigment yellow 139 is included: adding water into a reaction kettle, adding crude pigment yellow 139, pulping uniformly, heating to 150 ℃, treating for 5-10 hours under the pressure of 0.45MPa, cooling to 70 ℃, filtering, washing, drying and crushing to obtain a pigment yellow 139 product.
Further, the mass part ratio of the crude pigment yellow 139 to water is 1 (4-6).
For better understanding of the present invention, specific examples are given, and it should be emphasized that the above-described embodiments of the present invention are achieved and the problems described above are solved, without substantial difference between the effects of the examples and the various examples within the scope of the present invention;
in order to more intuitively show the advantages of the product, the invention is characterized in that the synthesis process of pigment yellow 139 comprises the following steps: synthesizing 1, 3-diiminoisoindoline by using phthalic anhydride and urea through a solid state melting method under the action of a catalyst, and synthesizing crude pigment yellow 139 through the reaction of the 1, 3-diiminoisoindoline and barbituric acid;
in contrast to comparative example 1 (a method for preparing c.i. pigment yellow 139 according to the national invention patent No. 201110447652.6 is incorporated by reference),
table 1: comparison of the Process influence of different 1, 3-diiminoisoindoline preparation methods on pigment yellow 139
From the above table, it can be seen that:
example 1 compares with comparative example 1: the difference 1 is that the preparation method of 1, 3-diiminoisoindoline (that is, phthalocyanine) is different, the comparative example I is prepared by a solvent method by using phthalonitrile,
the production process of the phthalonitrile is complex in route, high in production cost and relatively large in pollution, so that manufacturers are relatively few, environmental protection and safety are greatly affected in recent years, and the product supply is seriously insufficient.
The invention creatively utilizes a solid-state melting method to synthesize the 1, 3-diiminoisoindoline by phthalic anhydride and urea under the action of the catalyst, avoids the problem of phthalonitrile, and is beneficial to the large-scale production of pigment yellow 139.
In order to more intuitively show the technological advantages of the invention, the same technology is compared by adopting an equivalent replacement method,
comparative example 2:
the procedure in the preparation was the same as in comparative example 1, except that: in the preparation process of the comparative example, 1, 3-diiminoisoindoline is a fused crude product;
comparative example 3:
the procedure in the preparation was the same as in comparative example 1, except that: in the preparation process of the comparative example, the post-treatment was not cooled;
comparative example 4:
the procedure in the preparation was the same as in comparative example 1, except that: in the preparation process of the comparative example, 1, 3-diiminoisoindoline is a fused crude product;
and the test sample is detected by adopting the following detection method, and the detection result of cyanuric acid is shown in table 2:
1. preparation of cyanuric acid standard solution:
50mg of cyanuric acid standard substance is weighed, dissolved by using a mixed buffer solution of 0.005mol/L dipotassium hydrogen phosphate and 0.002mol/L monopotassium phosphate, transferred to a 500mL volumetric flask, added with 400mL buffer solution, dissolved by ultrasonic vibration, placed at room temperature and fixed in volume by using the buffer solution to obtain the cyanuric acid standard solution with the mass concentration of 100 mg/L.
2. Sample processing
400mg of the test sample prepared in the above examples and comparative examples is added with 0.005mol/L dipotassium hydrogen phosphate and 0.002mol/L potassium dihydrogen phosphate mixed buffer solution, heated to 60 ℃, filtered while hot, and filtered with a filter membrane of 0.45u, transferred to a 10mL volumetric flask, dissolved in a dissolution phase, diluted to a scale and shaken well.
3. Chromatographic detection conditions
Chromatographic column 250mm 4.0mm C18, volume ratio of mixed solution of 0.005mol/L dipotassium hydrogen phosphate and 0.002mol/L potassium dihydrogen phosphate to methanol in mobile phase is 95:5, the column temperature is 35 ℃, the flow rate is 0.8 mL/min, the detection wavelength is 213nm, and the sample injection amount is 20uL.
Table 2: comparison of different pigment yellow 139 synthesis processes
| Phthalocyanine derivative | Reaction system | Reactants | Post-treatment | Impurity species | Impurity content | |
| Example 1 | Refined product | Alcohol solution | Barbituric acid | Filtering and washing | Cyanuric acid | 11.14ppm |
| Example 2 | Melting the crude product | Alcohol solution | Barbituric acid | Filtering and washing | Cyanuric acid | 28.56ppm |
| Comparative example 1 | Refined product | Aqueous solution | Barbituric acid | Cooling, filtering and washing | Cyanuric acid | 16.75ppm |
| Comparative example 2 | Melting the crude product | Aqueous solution | Barbituric acid | Cooling, filtering and washing | Cyanuric acid | 360.42ppm |
| Comparative example 3 | Refined product | Water-solubleLiquid and its preparation method | Barbituric acid | Filtering and washing | Cyanuric acid | 5.23ppm |
| Comparative example 4 | Melting the crude product | Aqueous solution | Barbituric acid | Filtering and washing | Cyanuric acid | 8.06ppm |
From the above table, it can be seen that:
(1) Example 1 compares with example 2: the impurity cyanuric acid content in examples 1 and 2 is not very different, the pigment yellow 139 purity in the general examples 1 and 2 is higher, the impurity content is lower, the product purity is 98.5% and above, and the maximum single cyanuric acid impurity is controlled below 0.3%;
compared with the embodiment 1, the embodiment 2 omits the dehydration and drying process in the refining process of the 1, 3-diiminoisoindoline, shortens the process time and saves a great amount of energy consumption;
(2) Example 1 compares with comparative example 1:
in example 1: 1, 3-diiminoisoindoline is dissolved in alkaline methanol solution, so that the reaction is facilitated; particularly, the reaction system is methanol, a large amount of anhydrous solvent is added, residual acid waste water is very little along with the distillation of the methanol, and the waste liquid is very little and is easy to treat after the pressure filtration separation.
Comparative example 1, 3-diiminoisoindoline was reacted with a mixed solution of barbituric acid, acid and water for 1-2 hours, then heated to a reflux state, and kept in the reflux state for 2-5 hours, cooled, filtered to obtain a filter cake, which produced a large amount of wastewater, and had a great difficulty in treatment.
(3) Example 2 compares with comparative example 2:
comparative example 21, 3-diiminoisoindoline was reacted with a mixed solution of barbituric acid, acid and water for 1-2 hours, then warmed to a reflux state, maintained in the reflux state for 2-5 hours, cooled, filtered to obtain a filter cake, which produced a large amount of wastewater, and had a great difficulty in treatment.
In particular the cyanuric acid content of comparative example 2 was increased from 16.75ppm to 360.42ppm of comparative example 1,
this is probably due to the fact that the crude molten 1, 3-diiminoisoindoline is converted into cyanuric acid by side reactions of urea generated at high temperature during the melting,
the cyanuric acid content of comparative example 2 was increased from 28.56ppm to 360.42ppm in example 2, although the same as the crude molten 1, 3-diiminoisoindoline, the cyanuric acid content of example 2 could be maintained below 30ppm,
this is probably because the addition of the molten 1, 3-diiminoisoindoline of comparative example 2, the raw urea produced cyanuric acid as an impurity at high temperature, but cyanuric acid was not slightly soluble in cold water, and therefore, the filtration was cooled down under acidic conditions, resulting in a large amount of cyanuric acid remaining in the filter cake, leading to exceeding of cyanuric acid content, whereas the methanol system of example 2 was used, and the acid water was distilled in a small amount, and at this time, the cyanuric acid was dissolved in hot water by means of high temperature filtration, and cyanuric acid was discharged with hot water, and the cyanuric acid content of example 2 was maintained below 30 ppm.
In comparative examples 3 and 4, the heat filtration method is adopted in an equivalent alternative manner, the method can well solve the problem of high cyanuric acid content, can reduce the cyanuric acid content to below 10ppm, but the yield of pigment yellow 139 is reduced due to the higher solubility of pigment yellow 139 in hot water, and in order to maintain the cyanuric acid content to below 30ppm according to the temperature of the hot water, the yield of pigment yellow 139 is reduced by 10-15% relative to the cold water filtration,
in the embodiment 2, a methanol system is adopted, and acid water with a small dosage is distilled, at this time, a high-temperature filtering means is adopted, cyanuric acid is dissolved in hot water, and the cyanuric acid is discharged along with the hot water, so that the cyanuric acid content in the embodiment 2 can be maintained below 30ppm, the loss of pigment yellow 139 along with a large amount of hot water can be avoided, and the yield of the pigment yellow 139 is ensured.
To sum up: the invention creatively utilizes a solid-state melting method to synthesize the 1, 3-diiminoisoindoline by phthalic anhydride and urea under the action of the catalyst, avoids the problem of phthalonitrile, and is beneficial to the large-scale production of pigment yellow 139;
the molten 1, 3-diiminoisoindoline is adopted for direct reaction, so that the dehydration and drying process in the refining process of the 1, 3-diiminoisoindoline is omitted, the process time is shortened, and a large amount of energy consumption is saved;
the reaction system is methanol, a large amount of anhydrous solvent is added, and the residual acid wastewater is little along with the distillation of the methanol, so that the generation of a large amount of acid wastewater is avoided; by adopting the high-temperature filtering method, the cyanuric acid content can be maintained below 30ppm, the loss of pigment yellow 139 along with a large amount of hot water can be avoided, and the yield of pigment yellow 139 is ensured.
Claims (5)
1. The synthesis process of pigment yellow 139 is characterized by comprising the following steps:
(1) Synthesizing the adhesive melt of the 1, 3-diiminoisoindoline by using phthalic anhydride and urea in a solid state melting method in a batch mode or a continuous mode or a combination mode of batch and continuous modes under the action of a catalyst,
(2) Crude pigment yellow 139 was synthesized from the adhesive melt of 1, 3-diiminoisoindoline and barbituric acid;
the step (1): adding urea and ammonium salt into a reactor, heating to melt, adding a catalyst, dehydrating at 120-135 ℃ for 2-3 hours, slowly adding phthalic anhydride into the reactor after dehydrating, imidizing at 130-150 ℃ for 3 hours, continuously heating to 160-180 ℃ for 5-7 hours for condensation, vacuumizing after the condensation is completed, and cooling to below 60 ℃ to obtain an adhesive melt of 1, 3-diiminoisoindoline;
the step (2): adding alcohol and alkali into the adhesion melt of 1, 3-diiminoisoindoline, stirring and dissolving to be transparent, adding barbituric acid, heating and refluxing for reaction for 3 hours, adding sulfuric acid, adding benzoic acid, continuously heating and refluxing for reaction for 3-8 hours, distilling out methanol, filter-pressing and filtering, washing a filter cake to be neutral to obtain crude pigment yellow 139,
the catalyst in the step (1) is ammonium molybdate, the alcohol in the step (2) is methanol, and the alkali is sodium hydroxide.
2. The process for synthesizing pigment yellow 139 according to claim 1, wherein: in the step (1), the mass part ratio of urea, ammonium salt, catalyst and phthalic anhydride is (2-3): (1.5-2.5): (0.01-0.02): 1.
3. the process for synthesizing pigment yellow 139 according to claim 2, wherein: in the step (2), the mass part ratio of the 1, 3-diiminoisoindoline, the methanol, the sodium hydroxide, the barbituric acid, the sulfuric acid and the benzoic acid is 2.5: (65-75): (0.2-0.6): (1-1.5): (0.2-0.3): (0.1-0.3).
4. The process for synthesizing pigment yellow 139 according to claim 1, further comprising a refining step of crude pigment yellow 139: adding water into a reaction kettle, adding crude pigment yellow 139, pulping uniformly, heating to 150 ℃, treating for 5-10 hours under the pressure of 0.45MPa, cooling to 70 ℃, filtering, washing, drying and crushing to obtain a pigment yellow 139 product.
5. The process for synthesizing pigment yellow 139 according to claim 4, wherein the mass ratio of the crude pigment yellow 139 to water is 1:4.
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