CN117965053A - C.i. pigment red 57 for aqueous ink: 1 and a process for the preparation thereof - Google Patents
C.i. pigment red 57 for aqueous ink: 1 and a process for the preparation thereof Download PDFInfo
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- CN117965053A CN117965053A CN202410370453.7A CN202410370453A CN117965053A CN 117965053 A CN117965053 A CN 117965053A CN 202410370453 A CN202410370453 A CN 202410370453A CN 117965053 A CN117965053 A CN 117965053A
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- naphthoic acid
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- 235000010187 litholrubine BK Nutrition 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims description 12
- 238000002360 preparation method Methods 0.000 title abstract description 26
- 230000008569 process Effects 0.000 title description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 69
- ALKYHXVLJMQRLQ-UHFFFAOYSA-N 3-Hydroxy-2-naphthoate Chemical compound C1=CC=C2C=C(O)C(C(=O)O)=CC2=C1 ALKYHXVLJMQRLQ-UHFFFAOYSA-N 0.000 claims abstract description 50
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 20
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 20
- 150000004985 diamines Chemical class 0.000 claims abstract description 20
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims description 65
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 58
- 238000006243 chemical reaction Methods 0.000 claims description 55
- 239000000243 solution Substances 0.000 claims description 55
- 239000002904 solvent Substances 0.000 claims description 32
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 24
- 239000012074 organic phase Substances 0.000 claims description 24
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 24
- 238000004821 distillation Methods 0.000 claims description 21
- 230000008878 coupling Effects 0.000 claims description 20
- 238000010168 coupling process Methods 0.000 claims description 20
- 238000005859 coupling reaction Methods 0.000 claims description 20
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- 239000012954 diazonium Substances 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 16
- 239000012044 organic layer Substances 0.000 claims description 16
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 16
- 238000012360 testing method Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- RTIUWXJUJKDMPG-UHFFFAOYSA-N 7-formyl-3-hydroxynaphthalene-2-carboxylic acid Chemical compound O=CC1=CC=C2C=C(O)C(C(=O)O)=CC2=C1 RTIUWXJUJKDMPG-UHFFFAOYSA-N 0.000 claims description 12
- LTPSRQRIPCVMKQ-UHFFFAOYSA-N 2-amino-5-methylbenzenesulfonic acid Chemical compound CC1=CC=C(N)C(S(O)(=O)=O)=C1 LTPSRQRIPCVMKQ-UHFFFAOYSA-N 0.000 claims description 11
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 claims description 10
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000001110 calcium chloride Substances 0.000 claims description 10
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 229920002472 Starch Polymers 0.000 claims description 8
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 235000010288 sodium nitrite Nutrition 0.000 claims description 8
- 235000019698 starch Nutrition 0.000 claims description 8
- 239000008107 starch Substances 0.000 claims description 8
- 238000000605 extraction Methods 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 4
- 229910020889 NaBH3 Inorganic materials 0.000 claims description 2
- 239000000049 pigment Substances 0.000 abstract description 30
- 238000011161 development Methods 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 125000001033 ether group Chemical group 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 2
- 239000000976 ink Substances 0.000 description 28
- 238000006193 diazotization reaction Methods 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 3
- 239000012860 organic pigment Substances 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- -1 alkaline earth metal salt Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001739 density measurement Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention discloses a C.I. pigment red 57 for water-based ink, which comprises: 1 and a preparation method thereof, which belong to the technical field of pigment synthesis, wherein a macromolecular chain segment of polyethylene glycol diamine is grafted firstly through modification of 3-hydroxy-2-naphthoic acid, and then the modification of pigment is realized through combination of cyclodextrin and amino, on one hand, the polyethylene glycol diamine contains amino and ether groups, so that the hydrophilicity of the pigment is increased; on the other hand, polyethylene glycol diamine is a high molecular group, so that the dispersibility and adhesiveness of the pigment are improved, and the tinting strength of the pigment is improved; the invention prepares the C.I. pigment red 57 with good hydrophilicity and strong tinting strength for the water-based ink by modifying the pigment: 1, the preparation method is simple, is easy for large-scale production, and has good development prospect.
Description
Technical Field
The invention belongs to the technical field of pigment synthesis, and particularly relates to C.I. pigment red 57 for water-based ink, which comprises the following components: 1 and a preparation method thereof.
Background
C.i. pigment red 57:1 is red organic pigment prepared by diazotizing 4-aminotoluene-3-sulfonic acid, coupling with 2-hydroxy-3-naphthalene, and finally adding alkaline earth metal salt for laking. The pigment has bright color, strong tinting strength, acid and alkali resistance and good permeation resistance, and is widely used for tinting rubber, plastics, printing ink, paint and daily chemicals.
With the development of modern economic society and the perfection of environmental protection system, aqueous pigment became a hot spot of research, but c.i. pigment red 57:1 the organic pigment is difficult to disperse in water medium due to low surface polarity, so that the application of the organic pigment in water is limited. Thus, how to make pigment red 57: 1. modified to improve the dispersion in water to prepare the C.I. pigment red 57 for the water-based ink: 1 has great application value.
Disclosure of Invention
To solve the above problems, an object of the present invention is to provide a c.i. pigment red 57 for aqueous ink: 1 and a preparation method thereof.
The invention aims to achieve the aim, and the aim is achieved by the following technical scheme:
C.i. pigment red 57 for aqueous ink: 1, diazotizing 4-aminotoluene-3-sulfonic acid, coupling with 3-hydroxy-2-naphthoic acid derivative, and adding calcium chloride aqueous solution to carry out laking;
The 3-hydroxy-2-naphthoic acid derivative is prepared by reacting 7-formyl-3-hydroxy-2-naphthoic acid with polyethylene glycol diamine to generate an amine-terminated 3-hydroxy-2-naphthoic acid derivative, and grafting cyclodextrin.
The 3-hydroxy-2-naphthoic acid derivative is prepared by the following method:
1) Adding 7-formyl-3-hydroxy-2-naphthoic acid and polyethylene glycol diamine into an organic solvent, mixing and dissolving, stirring at 25-30 ℃ for reaction for 3-5 hours, adding a reducing agent into the mixture, continuing to react for 4-8 hours, removing the solvent by reduced pressure distillation after the reaction is finished, adding water into the obtained residue, adding dichloromethane for extraction for 2-3 times, merging organic phases, and removing the solvent by reduced pressure distillation of the organic phases to obtain an amine terminated 3-hydroxy-2-naphthoic acid derivative;
2) Adding the amine-terminated 3-hydroxy-2-naphthoic acid derivative, the cyclodextrin derivative and the potassium carbonate prepared in the step 1) into acetonitrile, stirring and dissolving, heating and refluxing for reaction for 8-15 h, filtering after the reaction is finished, and distilling the obtained filtrate under reduced pressure to remove a solvent to obtain the 3-hydroxy-2-naphthoic acid derivative.
The reducing agent in the step 1) is NaBH 4、NaBH3 CN or Et 3 SiH.
The organic solvent in the step 1) is methanol, ethanol or isopropanol.
The molecular weight of the polyethylene glycol diamine in the step 1) is 2000-4000.
The mass ratio of the 7-formyl-3-hydroxy-2-naphthoic acid, polyethylene glycol diamine, an organic solvent, a reducing agent, water and methylene dichloride in the step 1) is 1: 10-20: 30-50: 0.2 to 0.9: 20-40: 30-50.
The mass ratio of the amine terminated 3-hydroxy-2-naphthoic acid derivative, the cyclodextrin derivative, the potassium carbonate and the acetonitrile in the step 2) is 1:0.3 to 0.6: 0.05-0.08: 5-10.
The cyclodextrin derivative in the step 2) is prepared according to the following method:
Adding cyclodextrin and triethylamine into dichloromethane, stirring and mixing uniformly, cooling to 0-5 ℃, adding p-methylphenyl sulfonyl chloride into the mixture, heating to 10-20 ℃, reacting for 8-12 hours, adding the obtained reaction solution into water at 0-5 ℃, stirring and separating out an organic layer, washing the obtained organic layer with water until the pH value is 7, and removing a solvent by reduced pressure distillation of the obtained organic phase to obtain the cyclodextrin derivative.
The mass ratio of the cyclodextrin to the triethylamine to the dichloromethane to the p-methylphenyl sulfonyl chloride to the water is 1: 0.08-0.11: 5-10: 0.2-0.3: 5-10.
C.i. pigment red 57 for the aqueous ink: the preparation method of 1 comprises the following steps:
(1) Uniformly mixing 1 part of water and 0.5-0.6 part of 30% hydrochloric acid solution by weight, cooling to 0-5 ℃, adding 0.15-0.2 part of 4-aminotoluene-3-sulfonic acid, stirring and reacting for 0.5h, adding 0.45-0.55 part of 30% sodium nitrite solution by weight, and diazotizing for 0.6-0.8 h until Congo red test paper turns blue and potassium iodide starch test paper turns light blue, thus obtaining diazonium liquid;
(2) Adding 2.4-5.5 parts of 3-hydroxy-2-naphthoic acid derivative into 8-10 parts of ethanol, stirring and dissolving, adding 10-15 parts of water and 0.25-0.9 part of 30% sodium hydroxide solution, and stirring and mixing uniformly to obtain coupling solution;
(3) Dropwise adding the diazonium liquid prepared in the step (1) into the coupling liquid prepared in the step (2), continuously reacting for 0.5-1 h, adjusting the pH of a system to 8-8.5 by using sodium carbonate in the reaction process, adding 0.6-0.8 part by mass of 20-30% calcium chloride aqueous solution into the solution after the reaction is finished, heating to 80-90 ℃, stirring for 0.5-1 h, cooling, filtering, washing and drying to obtain the C.I. pigment red 57 for the water-based ink: 1.
Compared with the prior art, the invention has the following advantages:
the c.i. pigment red 57 for the water-based ink of the present invention: 1, modifying the pigment by modifying 3-hydroxy-2-naphthoic acid, firstly grafting polyethylene glycol diamine macromolecular chain segments, and then combining cyclodextrin with amino groups, wherein on one hand, the polyethylene glycol diamine contains amino groups and ether groups, so that the hydrophilicity of the pigment is increased; on the other hand, polyethylene glycol diamine is a high molecular group, so that the dispersibility and adhesiveness of the pigment are improved, and the tinting strength of the pigment is improved.
The c.i. pigment red 57 for the water-based ink of the present invention: the cyclodextrin is a molecule with a hollow structure, so that a stable inclusion complex can be formed, when the cyclodextrin interacts with pigment molecules, the hollow structure of the cyclodextrin can encapsulate the pigment molecules inside to form a structure similar to a microcapsule, and when metal ions are introduced to enable the cyclodextrin to form salt and lake, the pigment can be coated in a hydrophobic cavity of the cyclodextrin, so that the pigment is separated from an aqueous medium; on the other hand, the cyclodextrin surface contains a large amount of hydrophilic hydroxyl groups, so that the tension of the pigment surface is changed, the interaction force between the pigment and water is further increased, the hydrophilicity of the pigment is improved, and the dispersibility in water is increased.
The invention prepares the C.I. pigment red 57 with good hydrophilicity and strong tinting strength for the water-based ink by modifying the pigment: 1, the preparation method is simple, is easy for large-scale production, and has good development prospect.
Drawings
Fig. 1 is a c.i. pigment red 57 for aqueous ink prepared in example 3 of the present invention: 1 and comparative example dispersion map.
Detailed Description
The foregoing is further elaborated by the following description of embodiments of the present invention, which are given by way of example only, and should not be construed as limiting the scope of the present invention. All techniques implemented based on the above description of the invention are within the scope of the invention.
Example 1 preparation of cyclodextrin derivatives:
Adding 0.1kg of cyclodextrin and 0.008kg of triethylamine into 0.5kg of dichloromethane, stirring and mixing uniformly, cooling to 0 ℃, adding 0.02kg of p-methylphenyl sulfonyl chloride into the mixture, then heating to 10 ℃, reacting for 8 hours, adding the obtained reaction solution into water at 0 ℃, stirring and separating out an organic layer, washing the obtained organic layer with water until the pH value is 7, and removing a solvent by reduced pressure distillation of the obtained organic phase to obtain the cyclodextrin derivative.
Preparation of 3-hydroxy-2-naphthoic acid derivatives:
1) Adding 0.1kg of 7-formyl-3-hydroxy-2-naphthoic acid and 1kg of polyethylene glycol diamine into 3kg of methanol, stirring for reaction for 3 hours at 25 ℃ after mixing and dissolving, adding 0.02kg of NaBH 4 into the mixture, continuing to react for 4 hours, removing the solvent by reduced pressure distillation after the reaction is finished, adding 2kg of water into the obtained residue, adding 3kg of dichloromethane for extraction for 2 times, merging organic phases, and removing the solvent by reduced pressure distillation of the organic phases to obtain the amine-terminated 3-hydroxy-2-naphthoic acid derivative;
2) Adding 0.1kg of amine-terminated 3-hydroxy-2-naphthoic acid derivative, 0.03kg of cyclodextrin derivative and 0.005kg of potassium carbonate into 0.5kg of acetonitrile, stirring for dissolution, heating for reflux reaction for 8 hours, filtering after the reaction is finished, and distilling the obtained filtrate under reduced pressure to remove a solvent to obtain the 3-hydroxy-2-naphthoic acid derivative.
C.i. pigment red 57 for aqueous ink: 1, preparation:
(1) Uniformly mixing 1kg of water and 0.5kg of hydrochloric acid solution with the mass concentration of 30%, cooling to 0 ℃, adding 0.15kg of 4-aminotoluene-3-sulfonic acid, stirring and reacting for 0.5h, adding 0.45kg of sodium nitrite solution with the mass concentration of 30% for diazotization for 0.6h until Congo red test paper turns blue, and potassium iodide starch test paper turns light blue to obtain diazonium solution;
(2) Adding 2.4kg of 3-hydroxy-2-naphthoic acid derivative into 8kg of ethanol, stirring and dissolving, adding 10kg of water and 0.25kg of sodium hydroxide solution with mass concentration of 30%, and stirring and mixing uniformly to obtain coupling solution;
(3) Dropwise adding diazonium into coupling solution, continuously reacting for 0.5h, adjusting the pH of the system to 8 with sodium carbonate in the reaction process, adding 0.6kg of 20% calcium chloride aqueous solution into the solution after the reaction, heating to 80 ℃, stirring for 0.5h, cooling, filtering, washing and drying to obtain the C.I. pigment red 57 for the water-based ink: 1.
Example 2 preparation of cyclodextrin derivatives:
Adding 0.1kg of cyclodextrin and 0.009kg of triethylamine into 0.55kg of dichloromethane, stirring and mixing uniformly, cooling to 2 ℃, adding 0.022kg of p-methylphenyl sulfonyl chloride into the mixture, then heating to 13 ℃, reacting for 10 hours, adding the obtained reaction liquid into water at 2 ℃, stirring and separating out an organic layer, washing the obtained organic layer with water until the pH value is 7, and removing the solvent by reduced pressure distillation of the obtained organic phase to obtain the cyclodextrin derivative.
Preparation of 3-hydroxy-2-naphthoic acid derivatives:
1) Adding 0.1kg of 7-formyl-3-hydroxy-2-naphthoic acid and 1.2kg of polyethylene glycol diamine into 3.5kg of ethanol, stirring for reaction at 26 ℃ for 3.5 hours after the mixture is dissolved, adding 0.04kg of NaBH 3 CN into the mixture, continuing the reaction for 5 hours, removing the solvent by reduced pressure distillation after the reaction is finished, adding 2.5kg of water into the obtained residue, adding 3.5kg of dichloromethane for extraction for 2 times, merging organic phases, and removing the solvent by reduced pressure distillation of the organic phases to obtain an amino-terminated 3-hydroxy-2-naphthoic acid derivative;
2) Adding 0.1kg of amine-terminated 3-hydroxy-2-naphthoic acid derivative, 0.035kg of cyclodextrin derivative and 0.006kg of potassium carbonate into 0.6kg of acetonitrile, stirring for dissolution, heating and refluxing for reaction for 10 hours, filtering after the reaction is finished, and distilling the obtained filtrate under reduced pressure to remove a solvent to obtain the 3-hydroxy-2-naphthoic acid derivative.
C.i. pigment red 57 for aqueous ink: 1, preparation:
(1) Uniformly mixing 1kg of water and 0.52kg of hydrochloric acid solution with the mass concentration of 30%, cooling to 2 ℃, adding 0.16kg of 4-aminotoluene-3-sulfonic acid, stirring and reacting for 0.5h, adding 0.48kg of sodium nitrite solution with the mass concentration of 30% for diazotization for 0.65h until Congo red test paper turns blue, and potassium iodide starch test paper turns light blue to obtain diazonium solution;
(2) Adding 3kg of 3-hydroxy-2-naphthoic acid derivative into 8.5kg of ethanol, stirring and dissolving, adding 11kg of water and 0.4kg of sodium hydroxide solution with mass concentration of 30%, and stirring and mixing uniformly to obtain coupling solution;
(3) Dropwise adding diazonium into coupling liquid, continuously reacting for 0.6h, regulating the pH of the system to 8 by sodium carbonate in the reaction process, adding 0.65kg of 22% calcium chloride aqueous solution into the mixture after the reaction is finished, heating to 84 ℃, stirring for 0.65h, cooling, filtering, washing and drying to obtain the C.I. pigment red 57 for the water-based ink: 1.
Example 3 preparation of cyclodextrin derivatives:
Adding 0.1kg of cyclodextrin and 0.01kg of triethylamine into 0.65kg of dichloromethane, stirring and mixing uniformly, cooling to 3 ℃, adding 0.025kg of p-methylphenyl sulfonyl chloride into the mixture, heating to 15 ℃, reacting for 10 hours, adding the obtained reaction solution into 3 ℃ water, stirring and separating out an organic layer, washing the obtained organic layer with water until the pH value is 7, and removing the solvent by reduced pressure distillation of the obtained organic phase to obtain the cyclodextrin derivative.
Preparation of 3-hydroxy-2-naphthoic acid derivatives:
1) Adding 0.1kg of 7-formyl-3-hydroxy-2-naphthoic acid and 1.5kg of polyethylene glycol diamine into 4kg of ethanol, stirring for reaction for 4 hours at 28 ℃ after mixing and dissolving, adding 0.05kg of NaBH 4 into the mixture, continuing to react for 6 hours, removing the solvent by reduced pressure distillation after the reaction is finished, adding 3kg of water into the obtained residue, adding 4kg of dichloromethane for extraction for 3 times, merging organic phases, and removing the solvent by reduced pressure distillation of the organic phases to obtain the amine-terminated 3-hydroxy-2-naphthoic acid derivative;
2) Adding 0.1kg of amine-terminated 3-hydroxy-2-naphthoic acid derivative, 0.045kg of cyclodextrin derivative and 0.007kg of potassium carbonate into 0.8kg of acetonitrile, stirring and dissolving, heating and refluxing for reaction for 12 hours, filtering after the reaction is finished, and distilling the obtained filtrate under reduced pressure to remove a solvent to obtain the 3-hydroxy-2-naphthoic acid derivative.
C.i. pigment red 57 for aqueous ink: 1, preparation:
(1) Uniformly mixing 1kg of water and 0.55kg of hydrochloric acid solution with the mass concentration of 30%, cooling to 3 ℃, adding 0.18kg of 4-aminotoluene-3-sulfonic acid, stirring and reacting for 0.5h, adding 0.51kg of sodium nitrite solution with the mass concentration of 30% for diazotization for 0.7h until Congo red test paper turns blue, and potassium iodide starch test paper turns light blue to obtain diazonium solution;
(2) Adding 4kg of 3-hydroxy-2-naphthoic acid derivative into 9kg of ethanol, stirring and dissolving, adding 12kg of water and 0.6kg of sodium hydroxide solution with mass concentration of 30%, and stirring and mixing uniformly to obtain coupling solution;
(3) Dropwise adding diazonium into coupling solution, continuing to react for 0.8h, adjusting the pH of the system to 8.2 by sodium carbonate in the reaction process, adding 0.7kg of 25% calcium chloride aqueous solution with mass concentration into the solution after the reaction is finished, heating to 86 ℃, stirring for 0.75h, cooling, filtering, washing and drying to obtain the C.I. pigment red 57 for the water-based ink: 1.
Example 4 preparation of cyclodextrin derivatives:
Adding 0.1kg of cyclodextrin and 0.01kg of triethylamine into 0.8kg of dichloromethane, stirring and mixing uniformly, cooling to 4 ℃, adding 0.028kg of p-methylphenyl sulfonyl chloride into the mixture, then heating to 18 ℃, reacting for 11 hours, adding the obtained reaction solution into 4 ℃ water, stirring and separating out an organic layer, washing the obtained organic layer with water until the pH value is 7, and removing the solvent by reduced pressure distillation of the obtained organic phase to obtain the cyclodextrin derivative.
Preparation of 3-hydroxy-2-naphthoic acid derivatives:
1) Adding 0.1kg of 7-formyl-3-hydroxy-2-naphthoic acid and 1.8kg of polyethylene glycol diamine into 4.5kg of ethanol, stirring at 28 ℃ for reaction for 4.5 hours after the mixture is dissolved, adding 0.08kg of NaBH 4 into the mixture, continuing the reaction for 7 hours, removing the solvent by reduced pressure distillation after the reaction is finished, adding 3.5kg of water into the obtained residue, adding 4.5kg of dichloromethane for extraction for 3 times, merging organic phases, and removing the solvent by reduced pressure distillation of the organic phases to obtain an amino-terminated 3-hydroxy-2-naphthoic acid derivative;
2) Adding 0.1kg of amine-terminated 3-hydroxy-2-naphthoic acid derivative, 0.055kg of cyclodextrin derivative and 0.0075kg of potassium carbonate into 0.9kg of acetonitrile, stirring for dissolution, heating and refluxing for reaction for 14h, filtering after the reaction is finished, and distilling the obtained filtrate under reduced pressure to remove a solvent to obtain the 3-hydroxy-2-naphthoic acid derivative.
C.i. pigment red 57 for aqueous ink: 1, preparation:
(1) Uniformly mixing 1kg of water and 0.58kg of hydrochloric acid solution with the mass concentration of 30%, cooling to 4 ℃, adding 0.19kg of 4-aminotoluene-3-sulfonic acid, stirring and reacting for 0.5h, adding 0.53kg of sodium nitrite solution with the mass concentration of 30% for diazotization for 0.75h until Congo red test paper turns blue, and potassium iodide starch test paper turns light blue to obtain diazonium solution;
(2) Adding 5kg of 3-hydroxy-2-naphthoic acid derivative into 9.5kg of ethanol, stirring and dissolving, adding 14kg of water and 0.8kg of sodium hydroxide solution with mass concentration of 30%, and stirring and mixing uniformly to obtain coupling solution;
(3) Dropwise adding diazonium into coupling solution, continuously reacting for 0.9h, adjusting the pH of the system to 8.4 by sodium carbonate in the reaction process, adding 0.75kg of 28% calcium chloride aqueous solution with mass concentration into the solution after the reaction is finished, heating to 89 ℃, stirring for 0.9h, cooling, filtering, washing and drying to obtain the C.I. pigment red 57 for water-based ink: 1.
Example 5 preparation of cyclodextrin derivatives:
Adding 0.1kg of cyclodextrin and 0.011kg of triethylamine into 1kg of dichloromethane, stirring and mixing uniformly, cooling to 5 ℃, adding 0.03kg of p-methylphenyl sulfonyl chloride into the mixture, heating to 20 ℃, reacting for 12 hours, adding the obtained reaction solution into water at 5 ℃, stirring and separating an organic layer, washing the obtained organic layer with water until the pH value is 7, and distilling the obtained organic phase under reduced pressure to remove a solvent to obtain the cyclodextrin derivative.
Preparation of 3-hydroxy-2-naphthoic acid derivatives:
1) Adding 0.1kg of 7-formyl-3-hydroxy-2-naphthoic acid and 2kg of polyethylene glycol diamine into 5kg of isopropanol, stirring for reaction for 5 hours at 30 ℃ after mixing and dissolving, adding 0.09kg of Et 3 SiH into the mixture, continuing to react for 8 hours, removing the solvent by reduced pressure distillation after the reaction is finished, adding 4kg of water into the obtained residue, adding 5kg of dichloromethane for extraction for 3 times, merging organic phases, and removing the solvent by reduced pressure distillation of the organic phases to obtain the amine-terminated 3-hydroxy-2-naphthoic acid derivative;
2) Adding 0.1kg of amine-terminated 3-hydroxy-2-naphthoic acid derivative, 0.06kg of cyclodextrin derivative and 0.008kg of potassium carbonate into 1kg of acetonitrile, stirring and dissolving, heating and refluxing for reaction for 15h, filtering after the reaction is finished, and distilling the obtained filtrate under reduced pressure to remove a solvent to obtain the 3-hydroxy-2-naphthoic acid derivative.
C.i. pigment red 57 for aqueous ink: 1, preparation:
(1) Uniformly mixing 1kg of water and 0.6kg of hydrochloric acid solution with the mass concentration of 30%, cooling to 5 ℃, adding 0.2kg of 4-aminotoluene-3-sulfonic acid, stirring and reacting for 0.5h, adding 0.55kg of sodium nitrite solution with the mass concentration of 30% for diazotization for 0.8h until Congo red test paper turns blue, and potassium iodide starch test paper turns light blue to obtain diazonium solution;
(2) Adding 5.5kg of 3-hydroxy-2-naphthoic acid derivative into 10kg of ethanol, stirring and dissolving, adding 15kg of water and 0.9kg of sodium hydroxide solution with mass concentration of 30%, and stirring and mixing uniformly to obtain coupling solution;
(3) Dropwise adding diazonium into coupling liquid, continuing to react for 1h after dropwise adding, adjusting the pH of the system to 8.5 by using sodium carbonate in the reaction process, adding 0.8kg of 30% calcium chloride aqueous solution by mass concentration into the coupling liquid after the reaction is finished, heating to 90 ℃, stirring for 1h, cooling, filtering, washing and drying to obtain the C.I. pigment red 57 for the water-based ink: 1.
Example 6 preparation of cyclodextrin derivatives:
Adding 0.1kg of cyclodextrin and 0.011kg of triethylamine into 1kg of dichloromethane, stirring and mixing uniformly, cooling to 0 ℃, adding 0.02kg of p-methylphenyl sulfonyl chloride into the mixture, heating to 20 ℃, reacting for 10 hours, adding the obtained reaction solution into water at 5 ℃, stirring and separating an organic layer, washing the obtained organic layer with water until the pH value is 7, and removing a solvent by reduced pressure distillation of the obtained organic phase to obtain the cyclodextrin derivative.
Preparation of 3-hydroxy-2-naphthoic acid derivatives:
1) Adding 0.1kg of 7-formyl-3-hydroxy-2-naphthoic acid and 1kg of polyethylene glycol diamine into 5kg of ethanol, mixing and dissolving, stirring at 25 ℃ for reacting for 5 hours, adding 0.05kg of Et 3 SiH into the mixture, continuing reacting for 8 hours, distilling under reduced pressure to remove the solvent, adding 2kg of water into the obtained residue, adding 5kg of dichloromethane for extracting for 2 times, merging organic phases, and distilling the organic phases under reduced pressure to remove the solvent to obtain the amine-terminated 3-hydroxy-2-naphthoic acid derivative;
2) Adding 0.1kg of amine-terminated 3-hydroxy-2-naphthoic acid derivative, 0.05kg of cyclodextrin derivative and 0.008kg of potassium carbonate into 1kg of acetonitrile, stirring for dissolution, heating for reflux reaction for 8h, filtering after the reaction is finished, and distilling the obtained filtrate under reduced pressure to remove a solvent to obtain the 3-hydroxy-2-naphthoic acid derivative.
C.i. pigment red 57 for aqueous ink: 1, preparation:
(1) Uniformly mixing 1kg of water and 0.5kg of hydrochloric acid solution with the mass concentration of 30%, cooling to 5 ℃, adding 0.15kg of 4-aminotoluene-3-sulfonic acid, stirring and reacting for 0.5h, adding 0.5kg of sodium nitrite solution with the mass concentration of 30% for diazotization for 0.6h until Congo red test paper turns blue, and potassium iodide starch test paper turns light blue to obtain diazonium solution;
(2) Adding 2.4kg of 3-hydroxy-2-naphthoic acid derivative into 10kg of ethanol, stirring and dissolving, adding 15kg of water and 0.9kg of sodium hydroxide solution with mass concentration of 30%, and stirring and mixing uniformly to obtain coupling solution;
(3) Dropwise adding diazonium into coupling liquid, continuing to react for 1h after dropwise adding, adjusting the pH of the system to 8 by using sodium carbonate in the reaction process, adding 0.8kg of 20% calcium chloride aqueous solution by mass concentration into the solution after the reaction is finished, heating to 80 ℃, stirring for 1h, cooling, filtering, washing and drying to obtain the C.I. pigment red 57 for the water-based ink: 1.
C.i. pigment red 57 for the aqueous inks prepared in examples 1 to 6:1 performing a performance test wherein the tinting strength is measured according to the method in GB 1708-79; the colored light is detected according to the method in GB 1864-80; fluidity was measured according to the method in GB 1719-79; the bulk density measurement method comprises the following steps: accurately weighing 50g of pigment compound, placing into a measuring cylinder, sealing, oscillating up and down for 10 days, and recording the sample scale in the measuring cylinder; the transparency was measured in accordance with DIN 53163:1988 and the measurement results are shown in Table 1.
Table 1 Table of Performance parameters of the pigments prepared in examples 1 to 6
| Examples | Relative tinting strength (%) | Chromatic light | Fluidity/mm | Bulk density ml/50g | Transparency of the film |
| 1 | 99 | Yellow light | 41 | 25 | Preferably, it is |
| 2 | 100 | Yellow light | 43 | 24 | Preferably, it is |
| 3 | 105 | Yellow light | 44 | 24 | Preferably, it is |
| 4 | 100 | Yellow light | 42 | 24 | Preferably, it is |
| 5 | 99 | Yellow light | 40 | 26 | Preferably, it is |
| 6 | 100 | Yellow light | 42 | 25 | Preferably, it is |
As can be seen from the results in table 1, the c.i. pigment red 57 for water-based ink prepared by the present invention: 1, the pigment has strong tinting strength, large fluidity, small bulk density and better transparency, which indicates that the pigment has high dispersity, small particles and good dispersibility.
To verify the dispersibility in water of the pigment prepared according to the present invention, we used the c.i. pigment red 57 for the aqueous ink prepared in example 3: 1.30 g, dispersant CT-1111 1.2g and water 100g were mixed and milled at 2000r/min with stirring, and during milling, the dispersion was taken and the fineness change of the pigment at different milling times was measured with a blade fineness gauge. The comparative example used commercially available c.i. pigment red 57: 1. The detection results are shown in FIG. 1. As can be seen from the results of fig. 1, the c.i. pigment red 57 for water-based ink prepared according to the present invention: 1 as compared to commercially available c.i. pigment red 57:1, the fineness tends to be stable and smaller fineness is achieved after about 50min, which shows that compared with the pigment sold in the market, the pigment prepared by the invention is easier to disperse in water and has great application value.
While the foregoing describes the embodiments of the present invention, it is not intended to limit the scope of the present invention, and various modifications or variations may be made by those skilled in the art without the need for inventive effort on the basis of the technical solutions of the present invention.
Claims (9)
1. C.i. pigment red 57 for aqueous ink: 1, characterized in that: diazotizing 4-aminotoluene-3-sulfonic acid, coupling with 3-hydroxy-2-naphthoic acid derivative, and adding calcium chloride aqueous solution to carry out laking;
The 3-hydroxy-2-naphthoic acid derivative is prepared by reacting 7-formyl-3-hydroxy-2-naphthoic acid with polyethylene glycol diamine to generate an amine-terminated 3-hydroxy-2-naphthoic acid derivative, and grafting cyclodextrin.
2. The c.i. pigment red 57 for aqueous ink according to claim 1:1, characterized in that: the 3-hydroxy-2-naphthoic acid derivative is prepared by the following method:
1) Adding 7-formyl-3-hydroxy-2-naphthoic acid and polyethylene glycol diamine into an organic solvent, mixing and dissolving, stirring at 25-30 ℃ for reaction for 3-5 hours, adding a reducing agent into the mixture, continuing to react for 4-8 hours, removing the solvent by reduced pressure distillation after the reaction is finished, adding water into the obtained residue, adding dichloromethane for extraction for 2-3 times, merging organic phases, and removing the solvent by reduced pressure distillation of the organic phases to obtain an amine terminated 3-hydroxy-2-naphthoic acid derivative;
2) Adding the amine-terminated 3-hydroxy-2-naphthoic acid derivative, the cyclodextrin derivative and the potassium carbonate prepared in the step 1) into acetonitrile, stirring and dissolving, heating and refluxing for reaction for 8-15 h, filtering after the reaction is finished, and distilling the obtained filtrate under reduced pressure to remove a solvent to obtain the 3-hydroxy-2-naphthoic acid derivative.
3. The c.i. pigment red 57 for aqueous ink according to claim 2: 1, characterized in that: the reducing agent in the step 1) is NaBH 4、NaBH3 CN or Et 3 SiH; the organic solvent is methanol, ethanol or isopropanol.
4. The c.i. pigment red 57 for aqueous ink according to claim 2: 1, characterized in that:
The molecular weight of the polyethylene glycol diamine in the step 1) is 2000-4000.
5. The c.i. pigment red 57 for aqueous ink according to claim 2:1, characterized in that: the mass ratio of the 7-formyl-3-hydroxy-2-naphthoic acid, polyethylene glycol diamine, an organic solvent, a reducing agent, water and methylene dichloride in the step 1) is 1: 10-20: 30-50: 0.2 to 0.9: 20-40: 30-50.
6. The c.i. pigment red 57 for aqueous ink according to claim 2: 1, characterized in that: the mass ratio of the amine terminated 3-hydroxy-2-naphthoic acid derivative, the cyclodextrin derivative, the potassium carbonate and the acetonitrile in the step 2) is 1:0.3 to 0.6: 0.05-0.08: 5-10.
7. The c.i. pigment red 57 for aqueous ink according to claim 2: 1, characterized in that: the cyclodextrin derivative in the step 2) is prepared according to the following method:
Adding cyclodextrin and triethylamine into dichloromethane, stirring and mixing uniformly, cooling to 0-5 ℃, adding p-methylphenyl sulfonyl chloride into the mixture, heating to 10-20 ℃, reacting for 8-12 hours, adding the obtained reaction solution into water at 0-5 ℃, stirring and separating out an organic layer, washing the obtained organic layer with water until the pH value is 7, and removing a solvent by reduced pressure distillation of the obtained organic phase to obtain the cyclodextrin derivative.
8. The c.i. pigment red 57 for aqueous ink according to claim 7:1, characterized in that: the mass ratio of the cyclodextrin to the triethylamine to the dichloromethane to the p-methylphenyl sulfonyl chloride to the water is 1: 0.08-0.11: 5-10: 0.2-0.3: 5-10.
9. The c.i. pigment red 57 for aqueous ink of claim 1:1, which is characterized in that: the method comprises the following steps:
(1) Uniformly mixing 1 part of water and 0.5-0.6 part of 30% hydrochloric acid solution by weight, cooling to 0-5 ℃, adding 0.15-0.2 part of 4-aminotoluene-3-sulfonic acid, stirring and reacting for 0.5h, adding 0.45-0.55 part of 30% sodium nitrite solution by weight, and diazotizing for 0.6-0.8 h until Congo red test paper turns blue and potassium iodide starch test paper turns light blue, thus obtaining diazonium liquid;
(2) Adding 2.4-5.5 parts of 3-hydroxy-2-naphthoic acid derivative into 8-10 parts of ethanol, stirring and dissolving, adding 10-15 parts of water and 0.25-0.9 part of 30% sodium hydroxide solution, and stirring and mixing uniformly to obtain coupling solution;
(3) Dropwise adding the diazonium liquid prepared in the step (1) into the coupling liquid prepared in the step (2), continuously reacting for 0.5-1 h, adjusting the pH of a system to 8-8.5 by using sodium carbonate in the reaction process, adding 0.6-0.8 part by mass of 20-30% calcium chloride aqueous solution into the solution after the reaction is finished, heating to 80-90 ℃, stirring for 0.5-1 h, cooling, filtering, washing and drying to obtain the C.I. pigment red 57 for the water-based ink: 1.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4435543A1 (en) * | 1994-10-05 | 1996-04-11 | Hoechst Ag | Transparent strong yellow azo pigment as powder with large surface area - is based on C.I. Pigment Yellow 180 and is useful in electrophotographic toner and developer, powder lacquer and electret material |
| CN110117436A (en) * | 2018-02-06 | 2019-08-13 | 陕西奥华油墨科技有限公司 | Multi-functional environment-protection compound oil ink |
| CN110776777A (en) * | 2019-10-23 | 2020-02-11 | 安徽省卡乐优文化用品有限公司 | Water-based ink with good scratch resistance |
| CN116836567A (en) * | 2023-09-01 | 2023-10-03 | 蓬莱新光颜料化工有限公司 | Preparation method of dust-free pigment |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4435543A1 (en) * | 1994-10-05 | 1996-04-11 | Hoechst Ag | Transparent strong yellow azo pigment as powder with large surface area - is based on C.I. Pigment Yellow 180 and is useful in electrophotographic toner and developer, powder lacquer and electret material |
| CN110117436A (en) * | 2018-02-06 | 2019-08-13 | 陕西奥华油墨科技有限公司 | Multi-functional environment-protection compound oil ink |
| CN110776777A (en) * | 2019-10-23 | 2020-02-11 | 安徽省卡乐优文化用品有限公司 | Water-based ink with good scratch resistance |
| CN116836567A (en) * | 2023-09-01 | 2023-10-03 | 蓬莱新光颜料化工有限公司 | Preparation method of dust-free pigment |
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