CN114573998A - Pigment yellow 139 synthesis process - Google Patents
Pigment yellow 139 synthesis process Download PDFInfo
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- CN114573998A CN114573998A CN202210105657.9A CN202210105657A CN114573998A CN 114573998 A CN114573998 A CN 114573998A CN 202210105657 A CN202210105657 A CN 202210105657A CN 114573998 A CN114573998 A CN 114573998A
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- pigment yellow
- diiminoisoindoline
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- 239000000049 pigment Substances 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 52
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 14
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 13
- 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 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 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 22
- 239000004202 carbamide Substances 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 238000001914 filtration Methods 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
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 12
- 230000018044 dehydration Effects 0.000 claims abstract description 10
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000007670 refining Methods 0.000 claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 60
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 150000003863 ammonium salts Chemical class 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
- 238000001816 cooling Methods 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 13
- 238000010992 reflux Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 9
- 239000005711 Benzoic acid Substances 0.000 claims description 8
- 235000010233 benzoic acid Nutrition 0.000 claims description 8
- 239000012065 filter cake Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 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
- 238000009833 condensation Methods 0.000 claims description 6
- 230000005494 condensation Effects 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 5
- 239000000853 adhesive Substances 0.000 claims description 4
- 230000001070 adhesive effect Effects 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 238000004537 pulping Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 abstract description 32
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 230000009286 beneficial effect Effects 0.000 abstract description 6
- 150000002825 nitriles Chemical class 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
- 239000007787 solid Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 26
- 238000002360 preparation method Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000012043 crude product Substances 0.000 description 7
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 description 7
- 239000012535 impurity Substances 0.000 description 6
- 239000002351 wastewater Substances 0.000 description 6
- 229920006391 phthalonitrile polymer Polymers 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
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000007853 buffer solution Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 3
- 230000000694 effects Effects 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
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 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
- 230000007613 environmental effect Effects 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
- 239000012086 standard solution Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 125000003368 amide group Chemical group 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
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000706 filtrate Substances 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
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000000485 pigmenting effect Effects 0.000 description 1
- 239000002994 raw material Substances 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
- 238000005303 weighing Methods 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 synthesis process of pigment yellow 139, which belongs to the technical field of pigment production and comprises the following steps: the method is characterized in that a solid melting method is utilized, a batch type or a continuous type or a combination mode of the batch type and the continuous type is adopted, phthalic anhydride and urea are used for synthesizing 1, 3-diiminoisoindoline under the action of a catalyst, and the 1, 3-diiminoisoindoline and barbituric acid are reacted to synthesize crude pigment yellow 139. The invention has the beneficial effects that: the solid-state melting method uses phthalic anhydride and urea, avoids the problem of phthalic nitrile, and is beneficial to the large-scale production of pigment yellow 139; 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; by means of high-temperature filtration, the content of cyanuric acid can be maintained below 30ppm, 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.
Description
The technical field is as follows:
the invention belongs to the technical field of pigment production, and particularly relates to a synthesis process of pigment yellow 139.
Background art:
the pigment yellow 139, which is one of isoindoline pigments, has a molecular structure with more planarity due to the formation of intramolecular and intermolecular hydrogen bonds, which are caused by the presence of a carbonyl group, an imino group, a cyano group, an amide group, and the like in the molecule. Thus, pigment yellow 139 is an organic pigment having excellent heat and solvent resistance.
The preparation method of the pigment yellow 139 mainly comprises the following steps: in the presence of alkali, phthalic nitrile reacts in alcohol, and then the obtained intermediate reacts with barbituric acid compounds to obtain the target product.
For example, the national invention patent No. 201110447652.6 discloses a process for preparing c.i. pigment yellow 139. The method comprises the following steps
(1) A step of preparing 1, 3-diiminoisoindoline from phthalodinitrile;
(2) a step of preparing crude pigment yellow 139 by reacting 1, 3-diiminoisoindoline with barbituric acid;
(3) a step of pigmenting crude pigment yellow 139;
the invention not only improves the yield of C.I. pigment yellow 139, but also the obtained pigment has excellent properties such as high tinting strength, bright color, good dispersibility, excellent light fastness and weather fastness, etc.
However, the domestic phthalonitrile production process route is complex, the production cost is high, and the generated pollution is large, so that the number of manufacturers is relatively small, the environmental protection and safety influence is large in recent years, and the product supply is seriously insufficient.
The invention content is as follows:
in order to solve the problems and overcome the defects of 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 shortage of phthalonitrile supply.
The specific technical scheme for solving the technical problems comprises the following steps: the synthesis process of pigment yellow 139 is characterized by comprising the following steps:
(1) synthesizing 1, 3-diiminoisoindoline from phthalic anhydride and urea by a solid-state melting method in a batch mode or a continuous mode or a mode of combining the batch mode and the continuous mode under the action of a catalyst,
(2) crude pigment yellow 139 is synthesized by reacting 1, 3-diiminoisoindoline with barbituric acid.
Further, the step (1): adding urea and ammonium salt into a reactor, heating to be molten, adding a catalyst, dehydrating for 2-3 hours at the temperature of 120-135 ℃, adding phthalic anhydride after dehydration, carrying out imidization reaction for 3 hours at the temperature of 130-150 ℃, continuously heating to 160-180 ℃, keeping the temperature for 5-7 hours, condensing, cooling to below 60 ℃ after condensation is finished, adding water, stirring, adding sodium hydroxide until the materials are dissolved, separated out, dried, dehydrated and dried 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 for 2-3 hours at the temperature of 120-135 ℃, slowly adding phthalic anhydride into the reactor after dehydration, carrying out imidization reaction for 3 hours at the temperature of 130-150 ℃, continuously heating to 160-180 ℃, keeping the temperature for 5-7 hours, condensing, vacuumizing and cooling to below 60 ℃ after condensation is completed, thus obtaining the adhesive melt of 1, 3-diiminoisoindoline.
Further, the step (2): adding alcohol and alkali into 1, 3-diiminoisoindoline, stirring for dissolving until the solution is transparent, adding barbituric acid, heating for reflux reaction for 3 hours, adding sulfuric acid, adding benzoic acid, continuing heating for reflux reaction for 3-8 hours, distilling out methanol, performing filter pressing, washing a filter cake to be 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 of urea, ammonium salt, ammonium molybdate and phthalic anhydride are as follows: (2-3): (1.5-2.5): (0.01-0.02): 1.
further, in the step (2), the 1, 3-diiminoisoindoline, the methanol, the sodium hydroxide, the barbituric acid, the sulfuric acid and the benzoic acid are prepared in parts by weight 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 ℃, processing for 5-10 hours under the pressure of 0.45MPa, cooling to 70 ℃, filtering, washing, drying and crushing to obtain the pigment yellow 139 product.
Further, the mass part ratio of the crude pigment yellow 139 to the water is 1: 4.
The invention has the beneficial effects that:
the invention creatively utilizes a solid-state melting method to synthesize the 1, 3-diiminoisoindoline from phthalic anhydride and urea under the action of a catalyst, avoids the problem of phthalic nitrile 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 acidic wastewater is very little along with the distillation of the methanol, so that the generation of a large amount of waste acid water is avoided;
by means of high-temperature filtration, the content of cyanuric acid can be maintained below 30ppm, 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.
The specific implementation mode is as follows:
in the description of the invention, specific details are given only to enable a full understanding of the embodiments of the invention, but it should be understood by those skilled in the art that the invention is not limited to these details for the implementation. In other instances, well-known structures and functions have not been described or shown in detail to avoid obscuring the points of the embodiments of the invention. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
The specific implementation mode of the invention is as follows:
example 1:
the pigment yellow 139 synthesis process comprises the following steps:
(1) synthesizing 1, 3-diiminoisoindoline from phthalic anhydride and urea by a solid-state melting method in a batch mode or a continuous mode or a mode of combining the batch mode and the continuous mode under the action of a catalyst,
(2) crude pigment yellow 139 is synthesized by reacting 1, 3-diiminoisoindoline with barbituric acid.
The step (1) is specifically as follows:
adding urea and ammonium salt into a reactor, heating to be molten, adding a catalyst, dehydrating for 2-3 hours at the temperature of 120-135 ℃, adding phthalic anhydride after dehydration, carrying out imidization reaction for 3 hours at the temperature of 130-150 ℃, continuously heating to the temperature of 160-180 ℃, keeping the temperature for 5-7 hours, condensing, cooling to the temperature below 60 ℃ after condensation is finished, adding water, stirring, adding sodium hydroxide until the materials are dissolved, separated out, dried, dehydrated and dried to obtain 1, 3-diiminoisoindoline, wherein the catalyst is ammonium molybdate, and the mass ratio of the urea to the ammonium salt to the catalyst to the phthalic anhydride is as follows: (2-3): (1.5-2.5): (0.01-0.02): 1.
the ammonium salt can be ammonium nitrate, ammonium chloride inorganic ammonium salt, or organic ammonium salt.
The step (2) is specifically as follows:
adding alcohol and alkali into 1, 3-diiminoisoindoline, stirring for dissolving until the solution is transparent, adding barbituric acid, heating for reflux reaction for 3 hours, adding sulfuric acid, adding benzoic acid, continuing heating for reflux reaction for 3-8 hours, distilling out methanol, performing filter pressing, washing a filter cake to be neutral to obtain pigment yellow 139,
the mass parts of the 1, 3-diiminoisoindoline, the methanol, the alkali, the barbituric acid, the sulfuric acid and the benzoic acid are as follows: 2.5: (65-75): (0.2-0.6): (1-1.5): (0.2-0.6):(0.1-0.3).
Further, the refining process comprising crude pigment yellow 139: adding water into a reaction kettle, adding crude pigment yellow 139, pulping uniformly, heating to 150 ℃, processing for 5-10 hours under the pressure of 0.45MPa, cooling to 70 ℃, filtering, washing, drying and crushing to obtain the pigment yellow 139 product.
Further, the mass part ratio of the crude pigment yellow 139 to the water is 1 (4-6).
Example 2
The pigment yellow 139 synthesis process comprises the following steps:
(1) synthesizing 1, 3-diiminoisoindoline from phthalic anhydride and urea by a solid-state melting method in a batch mode or a continuous mode or a mode of combining the batch mode and the continuous mode under the action of a catalyst,
(2) the crude pigment yellow 139 is synthesized by the reaction of 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 the temperature of 120-135 ℃, slowly adding phthalic anhydride into the reactor after dehydration, carrying out imidization reaction for 3 hours at the temperature of 130-150 ℃, continuously heating to 160-180 ℃, keeping the temperature for 5-7 hours, condensing, vacuumizing and cooling to below 60 ℃ after condensation is completed, thus obtaining the 1, 3-diiminoisoindoline adhesive melt. The catalyst is ammonium molybdate, urea, and the mass portion ratio of ammonium salt, ammonium molybdate and phthalic anhydride is as follows: (2-3): (1.5-2.5): (0.01-0.02): 1.
the ammonium salt can be ammonium nitrate, ammonium chloride inorganic ammonium salt, or 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 3 hours, adding sulfuric acid, adding benzoic acid, continuously heating and refluxing for 3-8 hours, distilling out methanol, performing filter pressing, filtering, washing a filter cake to be neutral to obtain pigment yellow 139,
the 1, 3-diiminoisoindoline, methanol, alkali, barbituric acid, sulfuric acid and benzoic acid are prepared from the following components in parts by weight: 2.5: (65-75): (0.2-0.6): (1-1.5): (0.2-0.6):(0.1-0.3).
Further, the refining process comprising crude pigment yellow 139: adding water into a reaction kettle, adding crude pigment yellow 139, pulping uniformly, heating to 150 ℃, processing for 5-10 hours under the pressure of 0.45MPa, cooling to 70 ℃, filtering, washing, drying and crushing to obtain the pigment yellow 139 product.
Further, the mass part ratio of the crude pigment yellow 139 to the water is 1 (4-6).
In order to better understand the present invention, specific embodiments are described, it is emphasized that the effects of the embodiments are not substantially different from the various embodiments within the scope of the present invention, and the described effects of the present invention and the above-mentioned problems can be achieved;
in order to more intuitively show the advantages of the product, the invention is characterized in that the synthesis process of the pigment yellow 139 comprises the following steps: synthesizing 1, 3-diiminoisoindoline by using phthalic anhydride and urea under the action of a catalyst by using a solid state melting method, and synthesizing crude pigment yellow 139 by reacting the 1, 3-diiminoisoindoline with barbituric acid;
with comparative example 1 (incorporated by reference according to the national invention patent of the national invention patent No. 201110447652.6, a process for the preparation of c.i. pigment yellow 139),
table 1: comparison of effects of different preparation methods of 1, 3-diiminoisoindoline on pigment yellow 139 process
From the above table, it can be seen that:
example 1 compared to comparative example 1: the difference 1 is that 1, 3-diiminoisoindoline (i.e.phthalocyanine) is prepared by a solvent method using phthalodinitrile,
because the domestic phthalonitrile production process route of phthalonitrile is complex, the production cost is high, and the generated pollution is large, so that the production factories are relatively few, the environmental protection and safety influence is large in recent years, and the product supply is seriously insufficient.
The invention creatively utilizes a solid melting method to synthesize the 1, 3-diiminoisoindoline from phthalic anhydride and urea under the action of the catalyst, avoids the problem of phthalic nitrile and is beneficial to the large-scale production of the pigment yellow 139.
In order to more intuitively show the process advantages of the invention, the same process is compared by adopting an equivalent replacement method,
comparative example 2:
the procedure in the preparation process was the same as in comparative example 1, except that: in the preparation process of the comparative example, 1, 3-diiminoisoindoline is a molten crude product;
comparative example 3:
the procedure in the preparation process was the same as in comparative example 1, except that: in the preparation process of this comparative example, the post-treatment was not cooled;
comparative example 4:
the procedure in the preparation process is the same as in comparative example 1, except that: in the preparation process of the comparative example, 1, 3-diiminoisoindoline is a molten crude product;
the following detection method is adopted to detect the test sample, and the detection result of the cyanuric acid is shown in the table 2:
1. preparation of cyanuric acid standard solution:
weighing 50mg of cyanuric acid standard, dissolving the cyanuric acid standard by using a mixed buffer solution of 0.005mol/L dipotassium hydrogen phosphate and 0.002mol/L potassium dihydrogen phosphate, transferring the solution to a 500mL volumetric flask, adding 400mL of buffer solution, dissolving the solution by ultrasonic oscillation, standing the solution at room temperature, and fixing the 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 sample prepared in the above examples and comparative examples was taken, and a mixed buffer solution of 0.005mol/L dipotassium hydrogenphosphate and 0.002mol/L potassium dihydrogenphosphate was added thereto, heated to 60 ℃ and filtered while hot, and the filtrate was filtered through a 0.45u filter membrane and transferred to a 10mL volumetric flask, dissolved in the dissolved phase and diluted to the scale, and shaken up.
3. Chromatographic detection conditions
A chromatographic column 250mm 4.0mm C18, wherein the volume ratio of a mixed solution of 0.005mol/L dipotassium hydrogen phosphate and 0.002mol/L potassium dihydrogen phosphate to methanol in a 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 20 uL.
Table 2: comparison of Synthesis Processes for different pigment yellow 139
| Phthalocyanine | Reaction system | Reactants | Post-treatment | Species of impurities | Content of impurities | |
| 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 with water | 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 | Aqueous solution | Barbituric acid | Filtering and washing with water | Cyanuric acid | 5.23ppm |
| Comparative example 4 | Melting the crude product | Aqueous solution | Barbituric acid | Filtering and washing with water | Cyanuric acid | 8.06ppm |
From the above table, it can be seen that:
(1) example 1 compared to example 2: the content difference of the impurity cyanuric acid in the embodiment 1 and the embodiment 2 is not very large, the pigment yellow 139 in the general embodiment 1 and the embodiment 2 has higher purity and lower impurity content, the product purity is 98.5 percent and above, and the maximum single cyanuric acid impurity is controlled below 0.3 percent;
compared with the embodiment 1, the embodiment 2 omits a dehydration drying procedure in the refining process of the 1, 3-diiminoisoindoline, shortens the procedure time and saves a large amount of energy consumption;
(2) example 1 compared to comparative example 1:
in example 1: 1, 3-diiminoisoindoline is dissolved in alkaline methanol solution to facilitate reaction; particularly, the reaction system is methanol, a large amount of anhydrous solvent is added, the residual acidic wastewater is extremely little along with the distillation of the methanol, and the amount of the generated wastewater is small after filter pressing separation and is easy to treat.
Comparative example 1, 3-diiminoisoindoline is reacted with a mixed solution of barbituric acid, acid and water for 1-2 hours, then the temperature is raised to a reflux state, the reflux state is maintained for 2-5 hours, and cooling and filtering are carried out to obtain a filter cake, so that a large amount of waste water is generated, and the treatment difficulty is high.
(3) Example 2 compared to comparative example 2:
comparative example 21, 3-diiminoisoindoline is reacted with a mixed solution of barbituric acid, acid and water for 1-2 hours, then the temperature is raised to a reflux state, the reflux state is maintained for 2-5 hours, and cooling and filtering are carried out to obtain a filter cake, a large amount of waste water is generated, and the treatment difficulty is high.
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 because the urea is converted into cyanuric acid due to the side reaction caused by high temperature when the fused 1, 3-diiminoisoindoline crude product is fused,
the content of the cyanuric acid of the comparative example 2 is increased from 28.56ppm to 360.42ppm of the example 2, although the content of the cyanuric acid of the example 2 can be maintained below 30ppm while the content is the same as that of the fused 1, 3-diiminoisoindoline crude product,
this is probably because the molten 1, 3-diiminoisoindoline is added in the comparative example 2, the raw material urea can generate cyanuric acid impurity at high temperature, and the cyanuric acid is insoluble in cold acid and slightly soluble in cold water, so the cooling and filtering under the acidic condition can lead a large amount of cyanuric acid to remain in the filter cake, and the content of the cyanuric acid exceeds the standard, while the methanol system adopted in the example 2 is acid water with small dosage after distillation, at this time, the high-temperature filtering method is adopted, the cyanuric acid is dissolved in hot water, and the cyanuric acid is discharged along with the hot water, so the content of the cyanuric acid in the example 2 can be maintained below 30 ppm.
Comparative example 3 and comparative example 4, both of which adopt hot filtration in an equivalent replacement way, can well solve the problem of high content of cyanuric acid, and can reduce the content of cyanuric acid to below 10ppm, but because pigment yellow 139 has higher solubility in hot water, the yield of pigment yellow 139 is reduced, and according to the temperature of the hot water, in order to maintain the content of cyanuric acid to below 30ppm, the yield of pigment yellow 139 is reduced by 10-15% compared with that of cold water filtration,
in the embodiment 2, a methanol system is adopted, the distilled product is acid water with a small dosage, and at the moment, a high-temperature filtration method is adopted, cyanuric acid is dissolved in hot water and 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.
In summary, the following steps: the invention creatively utilizes a solid-state melting method to synthesize the 1, 3-diiminoisoindoline from phthalic anhydride and urea under the action of a catalyst, avoids the problem of phthalic nitrile 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, the residual acidic wastewater is very little along with the distillation of the methanol, and the generation of a large amount of waste acid water is avoided; by means of high-temperature filtration, the content of cyanuric acid can be maintained below 30ppm, 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.
Claims (8)
1. The synthesis process of pigment yellow 139 is characterized by comprising the following steps:
(1) synthesizing 1, 3-diiminoisoindoline from phthalic anhydride and urea by a solid-state melting method in a batch mode or a continuous mode or a mode of combining the batch mode and the continuous mode under the action of a catalyst,
(2) crude pigment yellow 139 is synthesized by reacting 1, 3-diiminoisoindoline with barbituric acid.
2. The process for synthesizing pigment yellow 139 according to claim 1, wherein the step (1):
adding urea and ammonium salt into a reactor, heating to be molten, adding a catalyst, dehydrating for 2-3 hours at the temperature of 120-135 ℃, adding phthalic anhydride after dehydration, carrying out imidization reaction for 3 hours at the temperature of 130-150 ℃, continuously heating to 160-180 ℃, keeping the temperature for 5-7 hours, condensing, cooling to below 60 ℃ after condensation is finished, adding water, stirring, adding sodium hydroxide until the materials are dissolved, separated out, dried, dehydrated and dried to obtain the 1, 3-diiminoisoindoline.
3. The process for synthesizing pigment yellow 139 according to claim 1, wherein the step (1):
adding urea and ammonium salt into a reactor, heating to melt, adding a catalyst, dehydrating for 2-3 hours at the temperature of 120-135 ℃, slowly adding phthalic anhydride into the reactor after dehydration, carrying out imidization reaction for 3 hours at the temperature of 130-150 ℃, continuously heating to 160-180 ℃, keeping the temperature for 5-7 hours, condensing, vacuumizing and cooling to below 60 ℃ after condensation is completed, thus obtaining the adhesive melt of 1, 3-diiminoisoindoline.
4. A process for the synthesis of pigment yellow 139 according to claim 2 or 3, characterized in that: the step (2):
adding alcohol and alkali into 1, 3-diiminoisoindoline, stirring for dissolving until the solution is transparent, adding barbituric acid, heating for reflux reaction for 3 hours, adding sulfuric acid, adding benzoic acid, continuing heating for reflux reaction for 3-8 hours, distilling out methanol, performing filter pressing, washing a filter cake to be 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.
5. The process for synthesizing pigment yellow 139 according to claim 4, wherein: in the step (1), the mass parts of urea, ammonium salt, catalyst and phthalic anhydride are as follows: (2-3): (1.5-2.5): (0.01-0.02): 1.
6. the process of synthesizing pigment yellow 139 according to claim 4, wherein: in the step (2), the 1, 3-diiminoisoindoline, the methanol, the sodium hydroxide, the barbituric acid, the sulfuric acid and the benzoic acid are prepared in parts by weight as follows: 2.5: (65-75): (0.2-0.6): (1-1.5): (0.2-0.3):(0.1-0.3).
7. The process for the synthesis of pigment yellow 139 according to claim 1, further comprising the step of refining the crude pigment yellow 139: adding water into a reaction kettle, adding crude pigment yellow 139, pulping uniformly, heating to 150 ℃, processing for 5-10 hours under the pressure of 0.45MPa, cooling to 70 ℃, filtering, washing, drying and crushing to obtain the pigment yellow 139 product.
8. The process for synthesizing pigment yellow 139 according to claim 7, wherein the mass part ratio of the crude pigment yellow 139 to water is 1: 4.
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| WO2023243354A1 (en) * | 2022-06-13 | 2023-12-21 | Dic株式会社 | Isoindoline compound |
| JP7552936B2 (en) | 2022-04-27 | 2024-09-18 | Dic株式会社 | Isoindoline Compounds |
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