A high-content red azo lake pigment preformulation and preparation method thereof
By adding modified chitosan and inorganic saline solution to color-calcination, the problem of low pigment content was solved, and a high content of red azo pigment preform was prepared, with high coloring power and stability. Suitable for coloring of various materials, improving the use performance and production efficiency of pigments.
Patent Information
- Application Number
- CN202411419600.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-12
- Publication Date
- 2024-12-20
- Estimated Expiration
- 2044-10-12
AI Technical Summary
The pigment content in existing pigment preforms is generally low, which affects the use efficiency and production cost, and leads to increasing the pigment content in pigment preforms being of great significance to improving the use performance and reducing production costs.
By adding modified chitosan to the crude red azo pigment compound obtained by coupling reaction and color-calcining in an inorganic saline solution, a high content of red azo pigment preform was prepared, and azelaic acid was used to prepare a cross-link network. The modified chitosan has good adsorption and dispersion, and improves the load and stability of the pigment.
The preparation of a high-content red azo pigment preform is achieved, with high tinting power, easy dispersion and stability. It is suitable for inks, coatings, plastics and other fields, improving the use performance and production efficiency of pigments.
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Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of pigment preparation, and in particular is a high-content red azo lake pigment preformulation and a preparation method thereof. Background Art
[0002] Pigment preformulation is a high-concentration dispersion of a single pigment, and the pigment is presented in the form of fine particles. Because the pigment is evenly dispersed, it has high tinting power, stable quality, bright colors, and reduces dust in the production process. It is increasingly used in the manufacture of masterbatches.
[0003] There are two main methods for preparing pigment preformulations: 1. In the production process of organic pigments, before the pigment particles are focused, the original liquid / solid phase is directly converted into the interface between the required carrier and the pigment by phase conversion, thereby obtaining a pigment preformulation; 2. A small amount of a carrier with good compatibility and necessary wetting and dispersing agents are used to completely disperse the pigment powder, and finally obtain a pigment preformulation. The commonly used carriers are PP (polypropylene) wax or PE (polyethylene) wax, but the pigment content in the prepared pigment preformulation is generally 40%~60%, which is generally low, thus affecting the efficiency and effect of the pigment and increasing the production cost. Therefore, increasing the pigment content in the pigment preformulation is of great significance to improving the performance of the pigment, reducing production costs and improving production efficiency. Summary of the invention
[0004] To solve the above problems, the object of the present invention is to provide a high-content red azo lake pigment preformulation and a preparation method thereof.
[0005] In order to achieve the above object, the present invention is implemented through the following technical solutions:
[0006] A high-content red azo pigment preformulation is prepared by adding modified chitosan to a crude red azo pigment compound obtained by coupling reaction, and then adding an inorganic salt aqueous solution for lake formation;
[0007] The modified chitosan is prepared according to the following steps:
[0008] 1) Add azelaic acid to an organic solvent, stir to dissolve, then add chitosan, stir to mix evenly, add diethyl azodicarboxylate and 1-hydroxybenzotriazole, react at 25-40°C for 3-8h, remove the solvent by reduced pressure distillation after the reaction is completed, wash the residue with a mixed solution of ethanol and n-hexane in a volume ratio of 1:1 for 3-5 times, and dry to obtain cross-linked chitosan;
[0009] 2) Add the cross-linked chitosan, pentaethylene glycol mono-p-toluenesulfonate and sodium hydride prepared in step 1) into tetrahydrofuran, stir and mix evenly, heat to 40-65° C. and react for 5-10 hours. After the reaction is completed, add water to quench the reaction, then add dichloromethane, separate the layers, and distill the obtained organic layer under reduced pressure to remove the solvent to obtain modified chitosan.
[0010] The organic solvent in step 1) is ether, ethanol or dichloromethane.
[0011] The chitosan deacetylation degree in step 1) is 85-90%.
[0012] The mass ratio of azelaic acid, organic solvent, chitosan, diethyl azodicarboxylate and 1-hydroxybenzotriazole in step 1) is 0.6-1:10-15:1:1.4-2:0.8-1.2.
[0013] The mass ratio of the cross-linked chitosan, pentaethylene glycol mono-p-toluenesulfonate, sodium hydride, tetrahydrofuran, water and dichloromethane in step 2) is 1:1.5~2:0.2~0.4:8~10:3~5:10~15.
[0014] The method for preparing the high-content red azo lake pigment preformulation comprises the following steps:
[0015] The crude red azo pigment compound obtained after the coupling reaction and the modified chitosan are added into water, stirred and dispersed for 0.5-1h, and then an inorganic salt aqueous solution with a mass concentration of 20-30% is added thereto, stirred for 1-2h, heated to 80-90°C, stirred for 0.5-1h, cooled, filtered, washed and dried to obtain a high-content red azo lake pigment preformulation.
[0016] The inorganic salt is calcium chloride, barium chloride or strontium chloride.
[0017] The mass ratio of the crude red azo pigment compound, the modified chitosan, water and the inorganic salt aqueous solution is 100:5-8:600-1000:150-250.
[0018] The red azo pigment crude compound obtained after the coupling reaction in the present invention is a pigment crude compound obtained after the coupling reaction is completed, filtered, and the obtained filter cake is dried.
[0019] Compared with the prior art, the present invention has the following advantages:
[0020] The high-content red azo lake pigment preformulation of the present invention uses azelaic acid to prepare a cross-linked reticular chitosan, and then a long ether chain is grafted on the side chain to prepare a modified chitosan, and the modified chitosan is used as a carrier to prepare a pigment preformulation. Chitosan has good adsorption, film-forming properties and biocompatibility, and the long ether chain grafted on the side chain can make the modified chitosan better dispersed in water. When in contact with the pigment crude compound, the adsorption effect and intermolecular force of chitosan are used to achieve the coating of the pigment crude product; in the process of adding inorganic salt lake, the pigment is deposited and coated in the hydrophobic reticular structure of the modified chitosan, and the amide group in the modified chitosan can form a hydrogen bond with the pigment, further improving the loading amount and stability of the pigment in the modified chitosan, thereby increasing the effective content of the pigment, and at the same time, the re-aggregation of the pigment particles can be avoided, and the dispersibility of the pigment is increased.
[0021] The high-content red azo pigment preformulation prepared by the invention has the advantages of high effective pigment content, strong tinting power, easy dispersion and high stability, and can be used for coloring in the fields of ink, coating, plastic and the like. DETAILED DESCRIPTION
[0022] In order to better understand the technical solution of the present invention, the above content of the present invention is further described in detail below through specific implementation methods in the form of embodiments, but this should not be understood as the scope of the above subject matter of the present invention being limited to the following examples. All technologies realized based on the above content of the present invention belong to the scope of the present invention.
[0023] Example 1 Preparation of modified chitosan:
[0024] 0.6 kg of azelaic acid was added to 10 kg of ether, and after stirring to dissolve, 1 kg of chitosan was added thereto, and after stirring and mixing evenly, 1.4 kg of diethyl azodicarboxylate and 0.8 kg of 1-hydroxybenzotriazole were added, and the mixture was reacted at 25°C for 8 hours. After the reaction was completed, the solvent was removed by distillation under reduced pressure, and the residue was washed three times with a mixed solution of ethanol and n-hexane in a volume ratio of 1:1, and dried to obtain cross-linked chitosan;
[0025] 1 kg of cross-linked chitosan, 1.5 kg of pentaethylene glycol mono-p-toluenesulfonate and 0.2 kg of sodium hydride were added into 8 kg of tetrahydrofuran, stirred and mixed evenly, heated to 40°C for reaction for 10 hours, and after the reaction was completed, 3 kg of water was added to quench the reaction, and then 10 kg of dichloromethane was added thereto, the layers were separated, and the obtained organic layer was distilled under reduced pressure to remove the solvent to obtain modified chitosan.
[0026] Preparation of high content red azo lake pigment preformulation:
[0027] 1 kg of the crude Pigment Red 57:1 compound obtained by the coupling reaction and 0.05 kg of modified chitosan were added to 6 kg of water, stirred and dispersed for 0.5 h, and then 2.5 kg of a 20% calcium chloride aqueous solution was added thereto. After stirring for 1 h, the mixture was heated to 80° C. and stirred for 0.5 h. The mixture was cooled, filtered, washed, and dried to obtain a high-content red azo lake pigment preformulation.
[0028] Example 2 Preparation of modified chitosan:
[0029] 0.7 kg of azelaic acid was added to 11 kg of ethanol, and after stirring to dissolve, 1 kg of chitosan was added thereto, and after stirring and mixing evenly, 1.5 kg of diethyl azodicarboxylate and 0.9 kg of 1-hydroxybenzotriazole were added, and the mixture was reacted at 30°C for 7 hours. After the reaction was completed, the solvent was removed by distillation under reduced pressure, and the residue was washed 5 times with a mixed solution of ethanol and n-hexane in a volume ratio of 1:1, and dried to obtain cross-linked chitosan;
[0030] 1 kg of cross-linked chitosan, 1.6 kg of pentaethylene glycol mono-p-toluenesulfonate and 0.25 kg of sodium hydride were added to 8.5 kg of tetrahydrofuran, stirred and mixed evenly, heated to 50°C for reaction for 8 hours, and after the reaction was completed, 3.5 kg of water was added to quench the reaction, and 11 kg of dichloromethane was added thereto, the layers were separated, and the obtained organic layer was distilled under reduced pressure to remove the solvent to obtain modified chitosan.
[0031] Preparation of high content red azo lake pigment preformulation:
[0032] 1 kg of the crude Pigment Red 53:1 compound obtained by the coupling reaction and 0.055 kg of modified chitosan were added to 7 kg of water, stirred and dispersed for 0.6 h, and then 1.5 kg of a 30% barium chloride aqueous solution was added thereto. After stirring for 1.5 h, the mixture was heated to 85° C., stirred for 0.6 h, cooled, filtered, washed, and dried to obtain a high-content red azo lake pigment preformulation.
[0033] Example 3 Preparation of modified chitosan:
[0034] 0.8 kg of azelaic acid was added to 12 kg of dichloromethane, and after stirring to dissolve, 1 kg of chitosan was added thereto, and after stirring and mixing evenly, 1.8 kg of diethyl azodicarboxylate and 1 kg of 1-hydroxybenzotriazole were added, and the mixture was reacted at 35°C for 6 hours. After the reaction was completed, the solvent was removed by distillation under reduced pressure, and the residue was washed 5 times with a mixed solution of ethanol and n-hexane in a volume ratio of 1:1, and dried to obtain cross-linked chitosan;
[0035] 1 kg of cross-linked chitosan, 1.8 kg of pentaethylene glycol mono-p-toluenesulfonate and 0.3 kg of sodium hydride were added to 9 kg of tetrahydrofuran, stirred and mixed evenly, heated to 55 ° C for 6 hours, and after the reaction was completed, 4 kg of water was added to quench the reaction, and then 12 kg of dichloromethane was added thereto, and the layers were separated. The obtained organic layer was distilled under reduced pressure to remove the solvent to obtain modified chitosan.
[0036] Preparation of high content red azo lake pigment preformulation:
[0037] 1 kg of the crude Pigment Red 57 compound obtained by the coupling reaction and 0.06 kg of modified chitosan were added to 8 kg of water, stirred and dispersed for 0.8 h, and then 2 kg of a 25% barium chloride aqueous solution was added thereto. After stirring for 1.5 h, the mixture was heated to 85° C., stirred for 0.7 h, cooled, filtered, washed, and dried to obtain a high-content red azo lake pigment preformulation.
[0038] Example 4 Preparation of modified chitosan:
[0039] 0.9 kg of azelaic acid was added to 14 kg of ethanol, and after stirring to dissolve, 1 kg of chitosan was added thereto, and after stirring and mixing evenly, 1.9 kg of diethyl azodicarboxylate and 1.1 kg of 1-hydroxybenzotriazole were added, and the mixture was reacted at 35°C for 5 hours. After the reaction was completed, the solvent was removed by distillation under reduced pressure, and the residue was washed 4 times with a mixed solution of ethanol and n-hexane in a volume ratio of 1:1, and dried to obtain cross-linked chitosan;
[0040] 1 kg of cross-linked chitosan, 1.9 kg of pentaethylene glycol mono-p-toluenesulfonate and 0.35 kg of sodium hydride were added into 9 kg of tetrahydrofuran, stirred and mixed evenly, heated to 60°C for reaction for 7 hours, and after the reaction was completed, 4.5 kg of water was added to quench the reaction, and 14 kg of dichloromethane was added thereto, the layers were separated, and the obtained organic layer was distilled under reduced pressure to remove the solvent to obtain modified chitosan.
[0041] Preparation of high content red azo lake pigment preformulation:
[0042] 1 kg of the crude compound of Pigment Red 53:1 obtained by the coupling reaction and 0.07 kg of modified chitosan were added to 8 kg of water, stirred and dispersed for 0.8 h, and then 2 kg of a 28% barium chloride aqueous solution was added thereto. After stirring for 1.8 h, the mixture was heated to 88° C., stirred for 0.8 h, cooled, filtered, washed, and dried to obtain a high-content red azo lake pigment preformulation.
[0043] Example 5 Preparation of modified chitosan:
[0044] 1 kg of azelaic acid was added to 15 kg of ether, and after stirring to dissolve, 1 kg of chitosan was added thereto, and after stirring and mixing evenly, 2 kg of diethyl azodicarboxylate and 1.2 kg of 1-hydroxybenzotriazole were added, and the mixture was reacted at 40°C for 3 hours. After the reaction was completed, the solvent was removed by distillation under reduced pressure, and the residue was washed 5 times with a mixed solution of ethanol and n-hexane in a volume ratio of 1:1, and dried to obtain cross-linked chitosan;
[0045] 1 kg of cross-linked chitosan, 2 kg of pentaethylene glycol mono-p-toluenesulfonate and 0.4 kg of sodium hydride were added into 10 kg of tetrahydrofuran, stirred and mixed evenly, heated to 65 ° C for reaction for 5 hours, and after the reaction was completed, 5 kg of water was added to quench the reaction, and then 15 kg of dichloromethane was added thereto, and the layers were separated. The obtained organic layer was distilled under reduced pressure to remove the solvent to obtain modified chitosan.
[0046] Preparation of high content red azo lake pigment preformulation:
[0047] 1 kg of the crude Pigment Red 48:2 compound obtained by the coupling reaction and 0.08 kg of modified chitosan were added to 10 kg of water, stirred and dispersed for 1 hour, and then 1.5 kg of a 20% barium chloride aqueous solution was added thereto. After stirring for 2 hours, the mixture was heated to 90° C., stirred for 1 hour, cooled, filtered, washed, and dried to obtain a high-content red azo lake pigment preformulation.
[0048] Example 6 Preparation of modified chitosan:
[0049] 1 kg of azelaic acid was added to 10 kg of dichloromethane, and after stirring to dissolve, 1 kg of chitosan was added thereto, and after stirring and mixing evenly, 1.6 kg of diethyl azodicarboxylate and 1.2 kg of 1-hydroxybenzotriazole were added, and the mixture was reacted at 40°C for 8 hours. After the reaction was completed, the solvent was removed by distillation under reduced pressure, and the residue was washed 5 times with a mixed solution of ethanol and n-hexane in a volume ratio of 1:1, and dried to obtain cross-linked chitosan;
[0050] 1 kg of cross-linked chitosan, 1.8 kg of pentaethylene glycol mono-p-toluenesulfonate and 0.4 kg of sodium hydride were added into 10 kg of tetrahydrofuran, stirred and mixed evenly, heated to 40°C for reaction for 5 hours, and after the reaction was completed, 5 kg of water was added to quench the reaction, and then 10 kg of dichloromethane was added thereto, the layers were separated, and the obtained organic layer was distilled under reduced pressure to remove the solvent to obtain modified chitosan.
[0051] Preparation of high content red azo lake pigment preformulation:
[0052] 1 kg of the crude Pigment Red 48:3 compound obtained by the coupling reaction and 0.07 kg of modified chitosan were added to 8 kg of water, stirred and dispersed for 0.9 h, and then 2 kg of a 25% mass concentration of strontium chloride aqueous solution was added thereto. After stirring for 2 h, it was heated to 90° C., stirred for 1 h, cooled, filtered, washed, and dried to obtain a high-content red azo lake pigment preformulation.
[0053] The high-content red azo lake pigment preformulations prepared in Examples 1 to 6 were tested respectively, wherein the tinting strength was tested according to the method in GB / T 5211.19-1988, the bulk density was tested according to the method in GB / T 21877-2015, the color light was tested according to the method in GB1864-89, and the transparency was tested according to the method in DIN 53163:1988. The test results are shown in Table 1.
[0054] Table 1 Performance parameter results of the pigment preformulations prepared in Examples 1 to 6
[0055]
[0056] It can be seen from the results in Table 1 that the high-content red azo lake pigment preformulation prepared by the present invention increases the pigment load and the content of the pigment preformulation due to the introduction of modified chitosan, and the prepared pigment preformulation has high tinting power, dispersibility and good transparency, and can be used for coloring in the fields of inks, coatings and plastics.
[0057] Although the above describes the specific implementation methods of the present invention, it does not limit the scope of protection of the present invention. Based on the technical solution of the present invention, various modifications or variations that can be made by those skilled in the art without creative work are still within the scope of protection of the present invention.
Claims
1. A high-content red azo lake pigment preformulation, characterized in that: The method is prepared by adding modified chitosan to the crude red azo pigment compound obtained by coupling reaction, and then adding an inorganic salt aqueous solution to perform color lake formation; The modified chitosan is prepared according to the following steps: 1) Add azelaic acid to an organic solvent, stir to dissolve, then add chitosan, stir to mix evenly, add diethyl azodicarboxylate and 1-hydroxybenzotriazole, react at 25-40°C for 3-8h, remove the solvent by reduced pressure distillation after the reaction is completed, wash the residue with a mixed solution of ethanol and n-hexane in a volume ratio of 1:1 for 3-5 times, and dry to obtain cross-linked chitosan; 2) adding the cross-linked chitosan, pentaethylene glycol mono-p-toluenesulfonate and sodium hydride prepared in step 1) into tetrahydrofuran, stirring and mixing evenly, heating to 40-65° C. to react for 5-10 hours, adding water to quench the reaction after the reaction is completed, and then adding dichloromethane to the mixture, separating the layers, and removing the solvent from the obtained organic layer by reduced pressure distillation to obtain modified chitosan; The inorganic salt is calcium chloride, barium chloride or strontium chloride.
2. The high-content red azo lake pigment preformulation according to claim 1, characterized in that: The organic solvent in step 1) is ether, ethanol or dichloromethane.
3. The high-content red azo lake pigment preformulation according to claim 1, characterized in that: The chitosan deacetylation degree in step 1) is 85-90%.
4. The high-content red azo lake pigment preformulation according to claim 1, characterized in that: The mass ratio of azelaic acid, organic solvent, chitosan, diethyl azodicarboxylate and 1-hydroxybenzotriazole in step 1) is 0.6-1:10-15:1:1.4-2:0.8-1.
2.
5. The high-content red azo lake pigment preformulation according to claim 1, characterized in that: The mass ratio of the cross-linked chitosan, pentaethylene glycol mono-p-toluenesulfonate, sodium hydride, tetrahydrofuran, water and dichloromethane in step 2) is 1:1.5~2:0.2~0.4:8~10:3~5:10~15.
6. A method for preparing the high-content red azo lake pigment preformulation according to claim 1, characterized in that: The following steps are involved: The crude red azo pigment compound obtained after the coupling reaction and the modified chitosan are added into water, stirred and dispersed for 0.5-1h, and then an inorganic salt aqueous solution with a mass concentration of 20-30% is added thereto, stirred for 1-2h, heated to 80-90°C, stirred for 0.5-1h, cooled, filtered, washed, and dried to obtain a high-content red azo lake pigment preformulation; The inorganic salt is calcium chloride, barium chloride or strontium chloride.
7. The method for preparing a high-content red azo lake pigment preformulation according to claim 6, characterized in that: The mass ratio of the crude red azo pigment compound, modified chitosan, water and inorganic salt aqueous solution is 100:5-8:600-1000:150-250.