CN103013159A - Method for anhydrously preparing isoindoline pigment - Google Patents
Method for anhydrously preparing isoindoline pigment Download PDFInfo
- Publication number
- CN103013159A CN103013159A CN2012105415810A CN201210541581A CN103013159A CN 103013159 A CN103013159 A CN 103013159A CN 2012105415810 A CN2012105415810 A CN 2012105415810A CN 201210541581 A CN201210541581 A CN 201210541581A CN 103013159 A CN103013159 A CN 103013159A
- Authority
- CN
- China
- Prior art keywords
- organic solvent
- diiminoisoindole
- reaction
- pigment
- barbituric acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000049 pigment Substances 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 17
- GWVMLCQWXVFZCN-UHFFFAOYSA-N isoindoline Chemical compound C1=CC=C2CNCC2=C1 GWVMLCQWXVFZCN-UHFFFAOYSA-N 0.000 title claims abstract description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- HNYOPLTXPVRDBG-UHFFFAOYSA-N barbituric acid Chemical compound O=C1CC(=O)NC(=O)N1 HNYOPLTXPVRDBG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 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 12
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 150000001298 alcohols Chemical class 0.000 claims description 5
- 150000001408 amides Chemical class 0.000 claims description 4
- 239000012188 paraffin wax Substances 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 17
- 238000005194 fractionation Methods 0.000 description 11
- 238000010792 warming Methods 0.000 description 9
- 238000001291 vacuum drying Methods 0.000 description 7
- 150000007524 organic acids Chemical class 0.000 description 5
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 229940093915 gynecological organic acid Drugs 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- NVKJOXRVEKMMHS-UHFFFAOYSA-N 5-nitro-1,2,4-triazol-3-one Chemical compound [O-][N+](=O)C1=NC(=O)N=N1 NVKJOXRVEKMMHS-UHFFFAOYSA-N 0.000 description 1
- 229910004373 HOAc Inorganic materials 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- ZGDPJFDIKFSDPR-UHFFFAOYSA-N acetic acid formic acid methanol hydrate Chemical compound O.OC.OC=O.CC(O)=O ZGDPJFDIKFSDPR-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000007520 diprotic acids Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000176 photostabilization Effects 0.000 description 1
- 230000000485 pigmenting effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000001052 yellow pigment 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention provides a method for anhydrously preparing an isoindoline pigment, comprising the following steps of: dissolving or suspending barbituric acid into an organic solvent A; adding an organic solvent B containing 1,3-diimino isoindoline to react; in a reaction process, fractionating generated ammonia gas; and then, collecting the isoindoline pigment from a reaction product. The method disclosed by the invention has the beneficial effects are very obvious; a pure organic solvent reaction system is adopted and a product yield is high; only the organic solvents need to be recycled; the production cost is low and the environmental pollution is small; and the method is convenient for industrial production.
Description
Technical field
The present invention relates to a kind of production technique of isoindoline yellow pigment.
Background technology
Isoindoline class pigment is owing to existing intermolecular, intramolecular hydrogen bond, and consists of solid netted piling up, and makes it to have good solvent resistance, resistance to migration, acid and alkali-resistance, resistance to oxidation reductibility and thermotolerance.In plastics, coating and printing ink, be used widely.Because such pigment is except indivedual documents, isoindoline class pigment is by 1,3-diiminoisoindole and barbituric acid and derivative thereof are synthetic, main intermediate 1, and the 3-diiminoisoindole can be that raw material is synthetic by containing substituting group phthalic nitrile or Tetra hydro Phthalic anhydride on the phenyl ring.
DE2041999 has reported the employing low-temp reaction, and heat treated mode prepares pigment in DMF/HOAc again, although this patent has used DMF to be solvent, has used organic acid in reaction process.US4166179 reported and made spent glycol, and water, formic acid (or diprotic acid of C4-C6) are as reaction system, and the pigment product that obtains is easily disperseed, and the transparency is good, and this patent has used formic acid as alkali-binding agent.US5091532 has reported that use phthalic nitrile and sodium methylate direct reaction (not passing into ammonia) obtain intermediate in the patent of Bayer, in methanol-water-formic acid (acetic acid) system, react preparation PY139 with barbituric acid again, but the pigment yield that adopts this method to obtain is low.The Ciba patent report a kind of synthetic method that improves the pigment opacifying power, under the organic solvent-free system, add glacial acetic acid as alkali-binding agent, stage by stage the synthetic PY139 of conditioned reaction temperature.Chinese patent CN200810139252.7 has reported that a kind of use organic acid is as alkali-binding agent and the synthetic PY139 of solvent, in building-up process, there is not the introducing of water, the crude product that is synthesized obtains tinting strength behind pigmenting high, and the oxidation-resistance in plastic applications and photostabilization all are improved, but this patent has been used a large amount of organic acids, will be a greatly test to the erosion resistance of equipment.
The above patent documentation of introducing all uses a large amount of organic acids, and it is large that this class organic acid has a consumption, and corrodibility is strong, price is high, and cost recovery is high and be difficult to whole recyclings, and product yield is at 70-80%, product yield is low, and by product is many, brings very large difficulty to wastewater treatment.
Summary of the invention
The purpose of this invention is to provide a kind of anhydrous method for preparing isoindoline pigment, the defects that exists to overcome prior art.
Method of the present invention comprises the steps:
With barbituric acid dissolving or be suspended in the organic solvent A, add the organic solvent B that contains 1,3-diiminoisoindole, at 50-140 ℃ of reaction 10-30h, fractionate out the ammonia of generation in the reaction process, then collect described isoindoline pigment from reaction product, its structural formula is as follows:
Wherein:
R
1, R
2, R
3, R
4Represent respectively H, the straight-chain paraffin of C1-C10 or branched paraffin;
R
5Represent NO
2-, Cl-, Br-, C
1-C
5Alkane etc.;
In the organic solvent A, the concentration of barbituric acid is 4～6g/100ml;
Contain among the organic solution B of 1,3-diiminoisoindole, the concentration of 1,3-diiminoisoindole is 9～15g/100ml;
Barbituric acid: 1,3-diiminoisoindole=1: 2.0～3.0, mol ratio;
Preferably, adopt the mode that drips, add the organic solution that contains 1,3-diiminoisoindole, time for adding is 10～60 minutes;
Organic solvent A and organic solvent B all are selected from amides, alcohols, dimethyl sulfoxide (DMSO) or N-Methyl pyrrolidone etc.;
Described amides is selected from DMF, N,N-dimethylacetamide or N, N-dimethyl propylene acid amides;
Described alcohols is selected from carbonatoms less than 10 alcoholic solvent, particular methanol, ethanol or ethylene glycol etc.;
The invention has the beneficial effects as follows fairly obviously, adopt pure organic solvent reaction system, product yield is high, only needs to reclaim organic solvent, and production cost is low, and environmental pollution is little, is convenient to suitability for industrialized production.
Embodiment
Embodiment 1
In reactor, add 800ml N, dinethylformamide, 37.5g(0.293 mole) barbituric acid, be warming up to 55 ℃ of dissolvings, in 30 minutes, be added dropwise to the 19.2g(0.132 mole) 1, the 3-diiminoisoindole is dissolved in the solution of 200ml DMF, reacted the ammonia that vacuum fractionation goes out to produce in the reaction process 30 hours.Be cooled to 20-30 ℃, filter, methanol wash, vacuum-drying obtains pigment 46g, yield 95%.
Embodiment 2
In reactor, add 800ml N, the N-N,N-DIMETHYLACETAMIDE, 37.5g(0.293 mole) barbituric acid, be warming up to 140 ℃ of dissolvings, in 30 minutes, be added dropwise to the 19.2g(0.132 mole) 1, the 3-diiminoisoindole is dissolved in the solution of 200ml N,N-dimethylacetamide, reaction 15h, the ammonia that vacuum fractionation goes out to produce in the reaction process.Be cooled to 20-30 ℃, filter, methanol wash, vacuum-drying obtains pigment 45g, yield 94%.
Embodiment 3
In reactor, add 800ml ethylene glycol, 37.5g(0.293 mole) barbituric acid, be warming up to 110 ℃ of dissolvings, in 30 minutes, be added dropwise to the 19.2g(0.132 mole) 1, the 3-diiminoisoindole is dissolved in 200ml ethylene glycol, reacted the ammonia that vacuum fractionation goes out to produce in the reaction process, the ammonia that vacuum fractionation goes out to produce in the reaction process 25 hours.Be cooled to 20-30 ℃, filter, methanol wash, vacuum-drying obtains pigment 45g, yield 94%.
Embodiment 4
In reactor, add 800ml methyl alcohol, 37.5g(0.293 mole) barbituric acid, be warming up to 55 ℃, dissolving was added dropwise to the 19.2g(0.132 mole in 30 minutes) 1, the 3-diiminoisoindole is dissolved in 200ml ethylene glycol, reacted 5 hours, vacuum fractionation is except ammonia in the reaction process.Be warming up to backflow, stirring reaction 30h, fractionation is except ammonia in the reaction process.Be cooled to 20-30 ℃, filter, methanol wash, vacuum-drying obtains pigment 43g, yield 90%.
Embodiment 5
In reactor, add 800ml DMF, 46.8g(0.293 mole) 1, the 3-dimethyl barbituric acid, be warming up to 110 ℃, dissolving was added dropwise to the 19.2g(0.132 mole in 30 minutes) 1, the 3-diiminoisoindole is dissolved in 200ml N, the solution of dinethylformamide reacted the ammonia that vacuum fractionation goes out in the reaction process 19 hours, the ammonia that vacuum fractionation goes out in the reaction process.Be cooled to 20-30 ℃, filter, methanol wash, vacuum-drying obtains pigment 43g, yield 90%.
Embodiment 6
In reactor, add 800ml N, dinethylformamide, 37.5g(0.293 mole) barbituric acid, be warming up to 55 ℃, dissolving was added dropwise to the 25.08g(0.132 mole in 30 minutes) 5-nitro-1, the 3-diiminoisoindole is dissolved in 200ml N, the solution of dinethylformamide reacted 30 hours, the ammonia that vacuum fractionation goes out to produce in the reaction process.Be cooled to 20-30 ℃, filter, methanol wash, vacuum-drying obtains pigment 46g, yield 95%.
Embodiment 7
In reactor, add 800ml methyl alcohol, 50.7g(0.396 mole) barbituric acid, be warming up to 55 ℃, dissolving was added dropwise to the 19.2g(0.132 mole in 30 minutes) 1, the 3-diiminoisoindole is dissolved in 200ml ethylene glycol, reacted 5 hours, vacuum fractionation is except ammonia in the reaction process.Be warming up to backflow, stirring reaction 30h, fractionation is except ammonia in the reaction process.Be cooled to 20-30 ℃, filter, methanol wash, vacuum-drying obtains pigment 43g, yield 95%.
Claims (7)
1. the anhydrous method for preparing isoindoline pigment, it is characterized in that, comprise the steps, with barbituric acid dissolving or be suspended in the organic solvent A, add the organic solvent B reaction that contains 1,3-diiminoisoindole, fractionate out the ammonia of generation in the reaction process, then collect described isoindoline pigment from reaction product, its structural formula is as follows:
Wherein:
R
1, R
2, R
3, R
4Represent respectively H, the straight-chain paraffin of C1-C10 or branched paraffin;
R
5Represent NO
2-, Cl-, Br-, C
1-C
5Alkane.
2. method according to claim 1 is characterized in that, at 50-140 ℃ of reaction 10-30h.
3. method according to claim 1 is characterized in that, in the organic solvent A, the concentration of barbituric acid is 4～6g/100ml; Contain among the organic solution B of 1,3-diiminoisoindole, the concentration of 1,3-diiminoisoindole is 9～15g/100ml.
4. method according to claim 1 is characterized in that, barbituric acid: 1,3-diiminoisoindole=1: 2.0～3.0, mol ratio.
5. method according to claim 1 is characterized in that, adopts the mode that drips, and adds the organic solution that contains 1,3-diiminoisoindole.
6. each described method is characterized in that according to claim 1～5, and organic solvent A and organic solvent B all are selected from amides, alcohols, dimethyl sulfoxide (DMSO) or N-Methyl pyrrolidone.
7. method according to claim 6 is characterized in that, described amides is selected from DMF, N,N-dimethylacetamide or N, N-dimethyl propylene acid amides;
Described alcohols is selected from carbonatoms less than 10 alcohols.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012105415810A CN103013159A (en) | 2012-12-13 | 2012-12-13 | Method for anhydrously preparing isoindoline pigment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012105415810A CN103013159A (en) | 2012-12-13 | 2012-12-13 | Method for anhydrously preparing isoindoline pigment |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103013159A true CN103013159A (en) | 2013-04-03 |
Family
ID=47962289
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012105415810A Pending CN103013159A (en) | 2012-12-13 | 2012-12-13 | Method for anhydrously preparing isoindoline pigment |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103013159A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114573998A (en) * | 2022-01-28 | 2022-06-03 | 山东世纪连泓新材料有限公司 | Pigment yellow 139 synthesis process |
| WO2023243354A1 (en) * | 2022-06-13 | 2023-12-21 | Dic株式会社 | Isoindoline compound |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4166179A (en) * | 1976-06-24 | 1979-08-28 | Basf Aktiengesellschaft | Manufacture of organic pigments |
| US4480097A (en) * | 1980-02-27 | 1984-10-30 | Basf Aktiengesellschaft | Isoindoline colorants |
| US4492796A (en) * | 1980-06-19 | 1985-01-08 | Bayer Aktiengesellschaft | Isoindolenine derivatives, processes for their preparation and their use as intermediate products for the preparation of dyestuffs |
| US5091532A (en) * | 1989-10-27 | 1992-02-25 | Bayer Aktiengesellschaft | Process for the preparation of pigments based on isoindole |
| CN102585542A (en) * | 2011-12-27 | 2012-07-18 | 百合花集团有限公司 | Method for preparing C.I. pigment yellow 139 |
-
2012
- 2012-12-13 CN CN2012105415810A patent/CN103013159A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4166179A (en) * | 1976-06-24 | 1979-08-28 | Basf Aktiengesellschaft | Manufacture of organic pigments |
| US4480097A (en) * | 1980-02-27 | 1984-10-30 | Basf Aktiengesellschaft | Isoindoline colorants |
| US4492796A (en) * | 1980-06-19 | 1985-01-08 | Bayer Aktiengesellschaft | Isoindolenine derivatives, processes for their preparation and their use as intermediate products for the preparation of dyestuffs |
| US5091532A (en) * | 1989-10-27 | 1992-02-25 | Bayer Aktiengesellschaft | Process for the preparation of pigments based on isoindole |
| CN102585542A (en) * | 2011-12-27 | 2012-07-18 | 百合花集团有限公司 | Method for preparing C.I. pigment yellow 139 |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114573998A (en) * | 2022-01-28 | 2022-06-03 | 山东世纪连泓新材料有限公司 | Pigment yellow 139 synthesis process |
| CN114573998B (en) * | 2022-01-28 | 2024-03-05 | 山东世纪连泓新材料有限公司 | Pigment yellow 139 synthesis process |
| WO2023243354A1 (en) * | 2022-06-13 | 2023-12-21 | Dic株式会社 | Isoindoline compound |
| JP7552935B2 (en) | 2022-06-13 | 2024-09-18 | Dic株式会社 | Isoindoline Compounds |
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Application publication date: 20130403 |