CN117924961A - Preparation method of C.I. pigment orange 68 - Google Patents
Preparation method of C.I. pigment orange 68 Download PDFInfo
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- CN117924961A CN117924961A CN202410066324.9A CN202410066324A CN117924961A CN 117924961 A CN117924961 A CN 117924961A CN 202410066324 A CN202410066324 A CN 202410066324A CN 117924961 A CN117924961 A CN 117924961A
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- benzimidazolone
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- pigment orange
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- 239000000049 pigment Substances 0.000 title claims abstract description 102
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000002262 Schiff base Substances 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- NECWXNDIPQKNCD-UHFFFAOYSA-N 5,6-diaminobenzimidazol-2-one Chemical compound C1=C(N)C(N)=CC2=NC(=O)N=C21 NECWXNDIPQKNCD-UHFFFAOYSA-N 0.000 claims abstract description 21
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims abstract description 21
- 239000001632 sodium acetate Substances 0.000 claims abstract description 21
- 235000017281 sodium acetate Nutrition 0.000 claims abstract description 21
- NTCCNERMXRIPTR-UHFFFAOYSA-N 2-hydroxy-1-naphthaldehyde Chemical compound C1=CC=CC2=C(C=O)C(O)=CC=C21 NTCCNERMXRIPTR-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000010668 complexation reaction Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims abstract description 15
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims abstract description 15
- 150000004753 Schiff bases Chemical class 0.000 claims abstract description 10
- 238000006482 condensation reaction Methods 0.000 claims abstract description 10
- 230000002378 acidificating effect Effects 0.000 claims abstract description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 31
- -1 benzimidazolone Schiff base Chemical class 0.000 claims description 30
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 29
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 239000003607 modifier Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical group C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 14
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 14
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 230000000536 complexating effect Effects 0.000 claims description 10
- 239000012065 filter cake Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 239000004094 surface-active agent Substances 0.000 claims description 10
- QOMNJPSRBRDQSU-UHFFFAOYSA-N 5-aminobenzimidazol-2-one Chemical compound C1=C(N)C=CC2=NC(=O)N=C21 QOMNJPSRBRDQSU-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- MBJIKIAWNPEHOR-UHFFFAOYSA-N 2,5,8,11,14-pentaoxabicyclo[13.4.0]nonadeca-1(15),16,18-triene-17-carbaldehyde Chemical compound O1CCOCCOCCOCCOC2=CC(C=O)=CC=C21 MBJIKIAWNPEHOR-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 150000001793 charged compounds Chemical class 0.000 claims description 6
- 239000012467 final product Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 238000001819 mass spectrum Methods 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 3
- 150000003384 small molecules Chemical class 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 238000002390 rotary evaporation Methods 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 abstract description 5
- 239000007788 liquid Substances 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 231100000331 toxic Toxicity 0.000 abstract description 3
- 230000002588 toxic effect Effects 0.000 abstract description 3
- 239000010815 organic waste Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 239000012153 distilled water Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
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- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
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- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- MYONAGGJKCJOBT-UHFFFAOYSA-N benzimidazol-2-one Chemical compound C1=CC=CC2=NC(=O)N=C21 MYONAGGJKCJOBT-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000001053 orange pigment Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
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Abstract
The invention provides a preparation method of C.I. pigment orange 68, which belongs to the technical field of pigment preparation, wherein 2-hydroxy-1-naphthaldehyde and 5, 6-diaminobenzimidazolone are subjected to condensation reaction in an acidic environment to prepare Schiff base, the prepared Schiff base is subjected to complexation reaction with nickel chloride and sodium acetate in the acidic environment, and after the complexation reaction is finished, the C.I. pigment orange 68 is obtained through post-treatment. Compared with the prior art, the method not only avoids the use of a toxic solvent DMF, but also reduces the temperature required by the reaction, can reduce the output of organic waste liquid, has low cost, is environment-friendly and safe to operate, and the prepared C.I. pigment orange 68 has the excellent characteristics of high hue saturation, high transparency, bright color, strong hydrophilicity, good dispersion stability and the like.
Description
Technical Field
The invention relates to the technical field of pigment preparation, in particular to a preparation method of C.I. pigment orange 68.
Background
The c.i. pigment orange 68 has a red color orange which has excellent thermal stability and weather resistance, and thus is widely used in industrial paint, automotive finishing, and plastics industries, and is also used in combination with the c.i. pigment orange 36 to improve the weather resistance of the c.i. pigment orange 36, and it is one of a few organic pigments suitable for high temperature polyamide resin coloring.
At present, the domestic market has little research on C.I. pigment orange 68 commodity, and a large amount of organic solvent is used in the preparation process, so that the production cost is increased, and the environment is polluted; in addition, as some technical links cannot break through, the field is monopolized by foreign big companies, and the required C.I. pigment orange 68 commodity is mostly dependent on import.
In the preparation of c.i. pigment orange 68 of formula (i), a benzimidazolone intermediate of formula (ii) is involved, which is typically prepared by condensing 2-hydroxy-1-naphthaldehyde with 5, 6-diaminobenzimidazolone. For example, german patent publication No. DE2263235A1 discloses a method for preparing c.i. pigment orange 68 by condensation under the environment of hydrochloric acid and ethylene glycol monomethyl ether and complexation under the environment of N, N-Dimethylformamide (DMF), specifically, 5, 6-diaminobenzimidazolone is dissolved in hydrochloric acid aqueous solution, then is dissolved in ethylene glycol monomethyl ether together with 2-hydroxy-1-naphthaldehyde, and is subjected to condensation reaction at 60-70 ℃, and is filtered, washed with methanol and dried to obtain benzimidazolone schiff base; suspending the obtained Schiff base in a large amount of DMF solution, adding nickel chloride dissolved in DMF, carrying out complexation reaction at a high temperature of 125 ℃, cooling to room temperature, sequentially carrying out suction filtration, DMF washing and water washing, and drying to obtain the product C.I. pigment orange 68. The Chinese patent application with publication number of CN103436047A discloses a method for preparing C.I. pigment orange 68 by dissolving in alkaline environment, adding hydrochloric acid for condensation and complexation, specifically adding potassium hydroxide into water, heating to 75 ℃, introducing nitrogen, sequentially adding 5, 6-diamino benzimidazolone and 2-naphthol-1-formaldehyde, reacting for a period of time, then adding 3-carboxylic acid-2-hydroxy-1-naphthaldehyde, adding hydrochloric acid for condensation reaction, directly adding nickel chloride aqueous solution into the solution for complexation reaction at a high temperature of 95-100 ℃, carrying out suction filtration, washing with water, drying, and recrystallizing with DMF to obtain the final dye.
However, in the two patents, a large amount of organic reagents such as DMF is adopted, the temperature required by the complexation reaction is high, the production cost is increased, the environment is seriously influenced, and the obtained product has dark color, low saturation, poor transparency and low tinting strength; therefore, there is a need to develop a c.i. pigment orange 68 synthesis process that is safe to operate, low in cost, and capable of reducing environmental pollution. In addition, since c.i. pigment orange 68 is a azomethine structure synthesized from 2-hydroxy-1-naphthaldehyde and 5, 6-diaminobenzimidazolone, a conventional modifier is not suitable for the pigment, and thus no report has been made on a modifier for c.i. pigment orange 68.
Disclosure of Invention
In order to solve the defects existing in the prior art, the invention provides the preparation method of the C.I. pigment orange 68, which avoids the use of a toxic solvent DMF, reduces the temperature of the complexation reaction, is environment-friendly and safe to operate, and the obtained C.I. pigment orange 68 product has excellent performance.
The technical scheme adopted by the invention is as follows:
a preparation method of the C.I. pigment orange 68 is that 2-hydroxy-1-naphthaldehyde and 5, 6-diaminobenzimidazolone are subjected to condensation reaction in an acidic environment to prepare Schiff base, the prepared Schiff base is subjected to complexation reaction with nickel chloride and sodium acetate in the acidic environment, and after the complexation reaction is finished, the C.I. pigment orange 68 is obtained through post-treatment.
Preferably, the preparation method of the C.I. pigment orange 68 has a synthetic route shown as a formula (III), and specifically comprises the following steps:
(1) Condensation reaction: under the protection of nitrogen, dissolving 2-hydroxy-1-naphthaldehyde into acetic acid to obtain 2-hydroxy-1-naphthaldehyde solution; dissolving 5, 6-diamino benzimidazolone in acetic acid solution to obtain 5, 6-diamino benzimidazolone solution; adding a 5, 6-diamino benzimidazolone solution into a 2-hydroxy-1-naphthaldehyde solution to obtain a reaction solution; heating the reaction solution to 60-65 ℃, reacting for 4-6 hours, then sequentially filtering, washing with hot water at 50-55 ℃ to be neutral, washing with methanol, and drying to obtain benzimidazolone Schiff base;
(2) Complexing reaction: adding the benzimidazolone Schiff base in the step (1) into water, stirring for 1-2 h, then adding sodium acetate, heating to 75-80 ℃, adding nickel chloride aqueous solution, preserving heat for 1-1.5 h, adding acetic acid, heating to 85-90 ℃, preserving heat for 2-3 h, cooling to 60 ℃, and sequentially filtering and washing to obtain a pigment filter cake;
(3) And (3) pigment post-treatment: adding the pigment filter cake obtained in the step (2) into water, stirring for 1-1.5 h, heating to 95 ℃, preserving heat for 1-1.5 h, and sequentially filtering, washing and drying to obtain C.I. pigment orange 68;
Preferably, the volume ratio of water to acetic acid in the reaction liquid in the step (1) is (2.9-3.1): 1.
Preferably, the molar ratio of the 5, 6-diamino benzimidazolone to the 2-hydroxy-1-naphthaldehyde is 1 (2-2.01).
Preferably, the molar ratio of the benzimidazolone Schiff base, the nickel chloride and the sodium acetate is 1 (1.2-1.3): 1-2.
Preferably, in the complexing reaction, the benzimidazolone Schiff base and the small molecular pigment modifier are added into water together and stirred, then the mixture is subjected to complexing reaction with nickel chloride and sodium acetate in an acidic environment, and after the complexing reaction is finished, the modified C.I. pigment orange 68 is obtained through post-treatment.
Preferably, the small molecule pigment modifier is (E) -5- (((4-benzo-15-crown ether-5 yl) methylene) amino) -benzimidazolone.
Further preferably, the amount of (E) -5- (((4-benzo-15-crown-5-yl) methylene) amino) -benzimidazolone is 2.5 to 3% by mass of the benzimidazolone Schiff base.
Preferably, the synthetic route of the (E) -5- (((4-benzo-15-crown-5-yl) methylene) amino) -benzimidazolone is shown in formula (IV):
Preferably, the preparation method of the (E) -5- (((4-benzo-15-crown ether-5 yl) methylene) amino) -benzimidazolone comprises the following steps: adding 4' -formyl benzo-15-crown-5 and 5-amino benzimidazolone into an organic solvent, stirring for 1-1.5 h at normal temperature, heating to reflux, preserving heat for 2.5-3.5 h, and performing reduced pressure rotary evaporation to obtain (E) -5- (((4-benzo-15-crown ether-5 yl) methylene) amino) -benzimidazolone.
Preferably, the organic solvent is methanol or ethanol; the molar ratio of the 4' -formyl benzo-15-crown-5 to the 5-amino benzimidazolone is (1-1.01): 1.
Preferably, the pigment press cake and the surfactant are added together into water and stirred at the time of pigment post-treatment.
Further preferably, the surfactant is naphthol polyoxyethylene ether and/or alkyl diphenyl ether disulfonate, wherein the chemical structure of the naphthol polyoxyethylene ether is shown as a formula (V), and the chemical structure of the alkyl diphenyl ether disulfonate is shown as a formula (VI):
Preferably, the dosage of the naphthol polyoxyethylene ether is 2-5% of the final product quality of the C.I. pigment orange 68, and the dosage of the alkyl diphenyl ether disulfonate is 1-5% of the final product quality of the C.I. pigment orange 68.
Further preferably, the alkyl diphenyl ether disulfonate and the naphthol polyoxyethylene ether are compounded according to the weight ratio of 1 (1-3), and the addition amount after compounding is 2-3% of the mass of the final product of the C.I. pigment orange 68.
A pigment modifier, which is named: (E) -5- (((4-benzo-15-crown-5-yl) methylene) amino) -benzimidazolone having the structural formula (VII):
wherein in the mass spectrum of the (E) -5- (((4-benzo-15-crown-5-yl) methylene) amino) -benzimidazolone, an [ M+H ] + molecular ion peak appears at M/z= 428.1860 and an [ M+Na ] + molecular ion peak appears at M/z= 450.1681.
The pigment modifier is applied to the modification of C.I. pigment orange 68.
Preferably, the method of application is to add (E) -5- (((4-benzo-15-crown-5-yl) methylene) amino) -benzimidazolone to the complexation reaction during the preparation of C.I. pigment orange 68 to modify C.I. pigment orange 68.
The invention has the beneficial effects that:
(1) The invention provides a method for preparing C.I. pigment orange 68 in a water phase system under the acid catalysis condition, which not only avoids the use of a toxic solvent DMF, but also can reduce the activation energy of reaction, accelerate the reaction rate, reduce the temperature required by the complexation reaction and reduce the output of organic waste liquid by adding acetic acid to form an acidic environment; compared with the prior art, the preparation method has the advantages of safe operation, low cost and less harm to the environment, and the prepared C.I. pigment orange 68 has bright color, high saturation, easy dispersion and excellent hydrophilicity.
(2) The invention also provides a pigment modifier, namely (E) -5- (((4-benzo-15-crown ether-5 group) methylene) amino) -benzimidazolone, which can be used for modifying the C.I. pigment orange 68, and the modified C.I. pigment orange 68 has strong tinting strength, good hydrophilicity and good dispersion stability.
(3) Sodium acetate is added in the preparation process of the C.I. pigment orange 68, so that on one hand, the dispersion and dissolution of Schiff base are facilitated, the reaction is promoted, and on the other hand, the sodium acetate can play a role in buffering in the reaction, so that the pH abrupt change of the reaction environment is prevented, and the reaction medium environment is more stable; in addition, the invention proves that the addition of sodium acetate can also improve the performances of the C.I. pigment orange 68 such as vividness, color light, tinting strength, hydrophilicity and the like.
Drawings
FIG. 1 is an infrared spectrum of (E) -5- (((4-benzo-15-crown-5-yl) methylene) amino) -benzimidazolone;
FIG. 2 is a mass spectrum of (E) -5- (((4-benzo-15-crown-5-yl) methylene) amino) -benzimidazolone;
FIG. 3 is a graph of the UV-visible absorption spectrum of (E) -5- (((4-benzo-15-crown-5-yl) methylene) amino) -benzimidazolone;
fig. 4 is a light transmittance line graph of c.i. pigment orange 68 prepared in examples 1 to 5 and comparative examples 1 to 3.
Detailed Description
The following description is made in connection with specific embodiments:
description of sources of experimental materials:
2-hydroxy-1-naphthaldehyde: purchased from Shanghai Michlin Biochemical technologies Co., ltd;
5, 6-diaminobenzimidazolone: purchased from zheng alpha chemical company, inc;
4' -formyl benzo-15-crown-5: purchased from zheng alpha chemical company, inc;
5-aminobenzimidazolone: purchased from Shanghai Michlin Biochemical technologies Co., ltd;
Naphthol polyoxyethylene ether: purchased from company of pigment auxiliary, company of Lianhong;
alkyl diphenyl ether disulfonate: purchased from chinese daily chemical institute;
Sodium acetate: purchased from Tianjin chemical reagent-works;
nickel chloride hexahydrate: purchased from Tianjin Fuchen reagent Co., ltd;
acetic acid: purchased from Tianjin northern Tianzhi chemical reagent plant;
Methanol: purchased from the tobacco stand far east fine chemical company, inc;
ethanol: purchased from the chemical industry company, buddha Shangsu Co., ltd;
DMF: purchased from the chemical industry company, buddha Shangsu Co., ltd;
And (3) a flat grinding instrument: model PM240, available from Shanghai modern instruments limited;
Color measuring instrument: model Datacolor 200LAV, available from Datacolor corporation;
contact angle measuring instrument: model OCA 15EC, available from Dataphysics company, germany;
Infrared spectrometer: model Nicolet IS50, available from Nicolet corporation of the united states;
Ultraviolet visible spectrometer: model UV2700, available from shimadzu corporation.
Example 1:
a preparation method of C.I. pigment orange 68, which comprises the following specific steps:
(1) Condensation reaction: under the protection of nitrogen, 10.32g of 2-hydroxy-1-naphthaldehyde is dissolved in 50mL of acetic acid to obtain 2-hydroxy-1-naphthaldehyde solution; 4.92g of 5, 6-diaminobenzimidazolone was dissolved in a solution prepared from 30mL of acetic acid and 240mL of distilled water to obtain a 5, 6-diaminobenzimidazolone solution;
Dropwise adding the 2-hydroxy-1-naphthaldehyde solution into the 5, 6-diamino benzimidazolone solution within 1h to obtain a reaction solution; the reaction solution is reacted for 6 hours at 65 ℃, filtered while the reaction solution is hot (the temperature at the beginning of the filtration should be ensured to be 50-60 ℃), washed to be neutral by hot water at 50 ℃, then washed by methanol, dried to obtain 13.58g of orange-red solid powder, namely benzimidazolone Schiff base;
(2) Complexing reaction: dispersing 5.45g of benzimidazolone Schiff base in the step (1) in 100mL of water, stirring and pulping for 1h, adding 0.95g of sodium acetate powder, and heating to 80 ℃ to obtain a suspension; dissolving 3.56g of nickel chloride hexahydrate in 20mL of distilled water to obtain a nickel chloride aqueous solution, slowly adding the nickel chloride aqueous solution into the suspension under stirring, preserving heat for 1h, adding 40mL of acetic acid, heating to 87 ℃, preserving heat for 2h, cooling to 60 ℃, filtering, and washing with water to obtain an orange-red filter cake (solid content is 30%), namely a pigment filter cake;
(3) And (3) pigment post-treatment: and (3) adding the pigment filter cake obtained in the step (2) into 100mL of distilled water, stirring and pulping for 1h, heating to 95 ℃, stirring and heat treating for 1h, and sequentially filtering, washing and drying to obtain 5.92g of orange powder, namely the C.I. pigment orange 68.
Example 2:
unlike example 1, 1.89g of sodium acetate powder was added in step (2); the rest of the procedure is the same as in example 1.
Example 3:
Unlike example 1, in step (2), 5.45g of benzimidazolone Schiff base was added, dispersed in 100mL of water, then 0.137g of (E) -5- (((4-benzo-15-crown-5-yl) methylene) amino) -benzimidazolone was added, and stirred and beaten for 1h; the rest of the procedure is the same as in example 1.
Wherein the preparation method of the (E) -5- (((4-benzo-15-crown ether-5 group) methylene) amino) -benzimidazolone comprises the following steps: 11.84g of 4' -formylbenzo-15-crown-5 and 5.94g of 5-aminobenzimidazolone were dispersed in 100mL of ethanol and stirred well to form a homogeneous condensate, stirred at room temperature for 1h, reacted at reflux for 3h and distilled under reduced pressure to give 14.68g of brown (E) -5- (((4-benzo-15-crown-5-yl) methylene) amino) -benzimidazolone, which was identified and related patterns are shown in FIGS. 1 to 3:
FIG. 1 is an infrared spectrum of (E) -5- (((4-benzo-15-crown-5-yl) methylene) amino) -benzimidazolone, as seen in IR (KBr, cm -1)νmax: 3178,2858,1709,1597,1512,1277,1134).
FIG. 2 is a mass spectrum of (E) -5- (((4-benzo-15-crown-5-yl) methylene) amino) -benzimidazolone, showing the [ M+H ] + molecular ion peak at M/z= 428.1860 and the [ M+Na ] + molecular ion peak at M/z= 450.1681, consistent with the calculated molecular weight; this demonstrates that the molecular weight of (E) -5- (((4-benzo-15-crown-5-yl) methylene) amino) -benzimidazolone is correct.
FIG. 3 is a graph of the UV-visible absorption spectrum of (E) -5- (((4-benzo-15-crown-5-yl) methylene) amino) -benzimidazolone, from which it is seen that an absorption peak of pi-pi electron transitions where C=N is conjugated to the benzene ring occurs at 350nm and that N-pi electron transitions where C=O on 5-aminobenzimidazolone occurs at 318nm, which is red shifted compared to 5-aminobenzimidazolone due to the increase of the conjugated chain of the product; the absorption peak at 265nm is the absorption peak of electron transition of fine structure pi-pi of benzene ring, and red shift occurs compared with 5-amino benzimidazolone; the above features indicate that c=o has been converted to c=n, (E) -5- (((4-benzo-15-crown-5-yl) methylene) amino) -benzimidazolone was successfully prepared.
Example 4:
unlike example 3, in step (3), the pigment cake was added to 100mL of distilled water, then 0.164g of naphthol polyoxyethylene ether (eo=20) was added, stirred and beaten for 1 hour, heated to 95 ℃ and stirred and heat-treated for 1 hour; the rest of the procedure is the same as in example 3.
Example 5:
Unlike example 3, in step (3), the pigment cake was added to 100mL of distilled water, and then a complex solution composed of naphthol polyoxyethylene ether (eo=20) and alkyl diphenyl ether disulfonate was added, stirred and beaten for 1 hour, heated to 95 ℃, and stirred and thermally treated for 1 hour; the rest of the procedure is the same as in example 3;
Wherein, the compound solution is prepared by adding 0.082g of naphthol polyoxyethylene ether (EO=20) and 0.082g of alkyl diphenyl ether disulfonate into 5mL of deionized water and performing ultrasonic treatment for 5min.
Comparative example 1:
The comparative example adopts the preparation method in the invention patent DE2263235A1, and the specific steps are as follows:
(1) Condensation reaction: 3.28g of 5, 6-diamino benzimidazolone and 4.06g of 36% hydrochloric acid are dissolved in 40mL of distilled water, slowly and jointly dissolved with 6.88g of 2-hydroxy-1-naphthaldehyde in 100mL of 2-methoxyethanol under the condition of stirring, condensation reaction is carried out for 1h at room temperature, then the reaction is continued for 1h at 65 ℃, filtering and methanol washing are carried out in sequence, an orange-red filter cake is obtained, and the filter cake is dried, so as to obtain benzimidazolone Schiff base;
(2) Complexing reaction: suspending 4.2g of the benzimidazolone Schiff base in the step (1) in 150mL of DMF to obtain a benzimidazolone Schiff base suspension; 2.2g of nickel chloride hexahydrate is dissolved in 150mL of DMF to obtain nickel chloride solution; adding nickel chloride solution into the benzimidazolone Schiff base suspension, carrying out metal complexation reaction for 2 hours at 125 ℃, cooling to room temperature, filtering, washing with DMF and water in sequence, and drying to obtain the C.I. pigment orange 68.
Comparative example 2:
The comparative example adopts the preparation method in the invention patent CN103436047A, and the specific steps are as follows:
In a 500mL four-necked flask, 160mL of distilled water is added, stirring is started, 8g of potassium hydroxide is carefully added, the temperature is raised to 75 ℃, nitrogen is introduced, 4.1g (0.025 mol) of 5, 6-diaminobenzimidazolone and 4.3g (0.025 mol) of 2-naphthol-1-formaldehyde are sequentially added, after 15min of reaction, 4.3g (0.025 mol) of 2-naphthol-1-formaldehyde and 0.01g of hyperdispersant BYK-W996 are added, stirring is continued for 15min, 14.2g of 36% hydrochloric acid is added, the material becomes dark red, stirring is carried out for 30min at 75-80 ℃, 6.66g (0.028 mol) of nickel chloride hexahydrate is added in 35mL of hot water, the material is carefully raised to 95-100 ℃, the temperature is kept for 18h, the temperature is reduced to 60 ℃, filtering is carried out, the filtrate is washed neutral by 80 ℃ of hot water, the filter cake is dried at 105 ℃, and then C.I. pigment orange 68 is obtained by DMF recrystallization.
Comparative example 3:
Unlike example 1, this comparative example does not add sodium acetate in the complexation reaction of step (2); the rest of the procedure is the same as in example 1.
Commercial properties of the c.i. pigment orange 68 products obtained in examples 1 to 5 and comparative examples 1 to 3 were examined, specifically as follows:
(1) Detection of color light, tinting strength, and transparency:
0.30g of C.I. pigment orange 68 and 1mL of varnish were mixed and ground on a PM240 flatmill, the ground ink was scraped off, the transparency (transparency of the pigment coating) was observed, and the color measurement was performed on a color meter.
0.10G of C.I. pigment orange 68 and 1g of titanium pigment are mixed, 1mL of varnish is added, mixed grinding is carried out on a PM240 flat grinding instrument, and the scraped sample is subjected to a tinting strength test on a color meter.
The test results are shown in table 1 below:
TABLE 1 detection results of color light, tinting strength, and pigment clarity
Note that: DC is the difference of saturation (brilliance), DC > 0 represents that the sample is more brilliant than the standard sample, and DC < 0 represents that the sample is darker than the standard sample; DH is the difference in hue (hue), DH > 0 representing the sample being more yellow than the standard and DH < 0 representing the sample being more red than the standard for orange pigments.
From table 1:
① The c.i. pigment orange 68 obtained in examples 1 to 5 is significantly improved in vividness compared to comparative examples 1 to 3, and the pigment vividness in examples 4 to 5 is better with the addition of (E) -5- (((4-benzo-15-crown ether-5 yl) methylene) amino) -benzimidazolone modifier and naphthol polyoxyethylene ether (eo=20), alkyl diphenyl ether disulfonate surfactant; examples 1 to 2 showed an improvement in vividness (Dc) after sodium acetate addition, as compared with comparative example 3.
② The c.i. pigment orange 68 obtained in examples 1 to 5 was more yellow in color than comparative examples 1,3, and the pigment color in examples 4 to 5 was more yellow with the addition of the modifier and the surfactant; examples 1-2 showed a significant increase in color after the addition of sodium acetate compared to comparative example 3.
③ The c.i. pigment orange 68 obtained in examples 1 to 5 was higher in coloring power than comparative examples 1 to 3, and the coloring power was gradually increased with the addition of the modifier and the surfactant; examples 1-2 showed an increase in tinting strength of about 14.2% after the addition of sodium acetate, as compared to comparative example 3.
④ The c.i. pigment orange 68 obtained in examples 1 to 5 has an overall improved transparency compared to comparative examples 1 to 3, and the pigments of examples 4 to 5 have the best transparency with the addition of the modifier and the surfactant.
(2) Hydrophilicity test:
0.5g of C.I. pigment orange 68 was ground in a mortar, put into a die and pressed for 30s, contact angle test was performed on a contact angle tester, and the average value was recorded.
The test results are shown in table 2 below:
TABLE 2 contact angle test results
As can be seen from table 2, the c.i. pigment orange 68 obtained in examples 1 to 5 has a significantly reduced contact angle compared to comparative examples 1 to 3, which illustrates that the hydrophilicity of the pigment is greatly increased, and the hydrophilicity of the pigment is also significantly increased with the addition of the modifier and the surfactant; examples 1-2 showed a 3.6-13.9 decrease in contact angle after the addition of sodium acetate, which demonstrates a significant improvement in hydrophilicity of c.i. pigment orange 68 after the addition of sodium acetate, as compared to comparative example 3.
(3) And (3) detecting dispersibility:
Adding 15mL of distilled water into 30mg of C.I. pigment orange 68, and sufficiently dispersing the pigment by ultrasonic to obtain a C.I. pigment orange 68 solution; after standing for 1min, 1mL of the solution was sucked 1cm away from the liquid surface, and diluted with 3mL of distilled water. The transmittance of the c.i. pigment orange 68 solution was measured at 433nm with a spectrophotometer over time.
The test results are shown in table 3 below, and the line graph drawn from table 3 is shown in fig. 4:
TABLE 3 light transmittance test results
As can be seen from tables 3 and 4, the c.i. pigment orange 68 obtained in examples 1 to 5 has a smaller light transmittance as a whole than comparative examples 1 to 3, which shows that the pigment has a better dispersibility and dispersion stability, and the dispersibility is significantly improved with the addition of naphthol polyoxyethylene ether (eo=20) and alkyl diphenyl ether disulfonate surfactant.
Claims (10)
1. A preparation method of the C.I. pigment orange 68 is that 2-hydroxy-1-naphthaldehyde and 5, 6-diaminobenzimidazolone are subjected to condensation reaction in an acidic environment to prepare Schiff base, the prepared Schiff base is subjected to complexation reaction with nickel chloride and sodium acetate in the acidic environment, and after the complexation reaction is finished, the C.I. pigment orange 68 is obtained through post-treatment.
2. The method according to claim 1, wherein the synthetic route is represented by formula (iii), and specifically comprises the steps of:
(1) Condensation reaction: under the protection of nitrogen, dissolving 2-hydroxy-1-naphthaldehyde into acetic acid to obtain 2-hydroxy-1-naphthaldehyde solution; dissolving 5, 6-diamino benzimidazolone in acetic acid solution to obtain 5, 6-diamino benzimidazolone solution; adding a 5, 6-diamino benzimidazolone solution into a 2-hydroxy-1-naphthaldehyde solution to obtain a reaction solution; heating the reaction solution to 60-65 ℃, reacting for 4-6 hours, then sequentially filtering, washing with hot water at 50-55 ℃ to be neutral, washing with methanol, and drying to obtain benzimidazolone Schiff base;
(2) Complexing reaction: adding the benzimidazolone Schiff base in the step (1) into water, stirring for 1-2 h, then adding sodium acetate, heating to 75-80 ℃, adding nickel chloride aqueous solution, preserving heat for 1-1.5 h, adding acetic acid, heating to 85-90 ℃, preserving heat for 2-3 h, cooling to 60 ℃, and sequentially filtering and washing to obtain a pigment filter cake;
(3) And (3) pigment post-treatment: adding the pigment filter cake obtained in the step (2) into water, stirring for 1-1.5 h, heating to 95 ℃, preserving heat for 1-1.5 h, and sequentially filtering, washing and drying to obtain C.I. pigment orange 68;
3. the method according to claim 2, wherein the volume ratio of water to acetic acid in the reaction liquid in the step (1) is (2.9-3.1): 1;
Preferably, the molar ratio of the 5, 6-diamino benzimidazolone to the 2-hydroxy-1-naphthaldehyde is 1 (2-2.01);
preferably, the molar ratio of the benzimidazolone Schiff base, the nickel chloride and the sodium acetate is 1 (1.2-1.3): 1-2.
4. The method of claim 1, wherein the schiff base and the small-molecule pigment modifier are added into water together for stirring in the complexing reaction, then the mixture is subjected to the complexing reaction with nickel chloride and sodium acetate in an acidic environment, and after the complexing reaction is finished, the modified c.i. pigment orange 68 is obtained through post treatment;
preferably, the small molecule pigment modifier is (E) -5- (((4-benzo-15-crown ether-5 yl) methylene) amino) -benzimidazolone;
Further preferably, the amount of (E) -5- (((4-benzo-15-crown-5 yl) methylene) amino) -benzimidazolone is 2.5 to 3% by mass of the Schiff base.
5. The method of claim 4, wherein the synthetic route of (E) -5- (((4-benzo-15-crown-5-yl) methylene) amino) -benzimidazolone is shown in formula (iv):
Preferably, the preparation method of the (E) -5- (((4-benzo-15-crown ether-5 yl) methylene) amino) -benzimidazolone comprises the following steps: adding 4' -formyl benzo-15-crown-5 and 5-amino benzimidazolone into an organic solvent, stirring for 1-1.5 h at normal temperature, heating to reflux, preserving heat for 2.5-3.5 h, and performing reduced pressure rotary evaporation to obtain (E) -5- (((4-benzo-15-crown ether-5 yl) methylene) amino) -benzimidazolone.
6. The method of claim 5, wherein the organic solvent is methanol or ethanol; the molar ratio of the 4' -formyl benzo-15-crown-5 to the 5-amino benzimidazolone is (1-1.01): 1.
7. The method of claim 1, wherein the post-treatment is to add the pigment cake and the surfactant together into water and agitate;
Preferably, the surfactant is naphthol polyoxyethylene ether and/or alkyl diphenyl ether disulfonate, wherein the chemical structure of the naphthol polyoxyethylene ether is shown as a formula (V), and the chemical structure of the alkyl diphenyl ether disulfonate is shown as a formula (VI):
Preferably, the dosage of the naphthol polyoxyethylene ether is 2-5% of the final product quality of the C.I. pigment orange 68, and the dosage of the alkyl diphenyl ether disulfonate is 1-5% of the final product quality of the C.I. pigment orange 68;
further preferably, the alkyl diphenyl ether disulfonate and the naphthol polyoxyethylene ether are compounded according to the weight ratio of 1 (1-3), and the addition amount after compounding is 2-3% of the mass of the final product of the C.I. pigment orange 68.
8. A pigment modifier, which is named: (E) -5- (((4-benzo-15-crown-5-yl) methylene) amino) -benzimidazolone having the structural formula (VII):
wherein in the mass spectrum of the (E) -5- (((4-benzo-15-crown-5-yl) methylene) amino) -benzimidazolone, an [ M+H ] + molecular ion peak appears at M/z= 428.1860 and an [ M+Na ] + molecular ion peak appears at M/z= 450.1681.
9. Use of the pigment modifier of claim 8 for the modification of c.i. pigment orange 68.
10. The use according to claim 9, characterized in that the c.i. pigment orange 68 is modified by adding (E) -5- (((4-benzo-15-crown-5-yl) methylene) amino) -benzimidazolone to the complexation reaction during the preparation of c.i. pigment orange 68.
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