CN113999542A - Nano composite preparation of disperse dye and preparation method thereof - Google Patents
Nano composite preparation of disperse dye and preparation method thereof Download PDFInfo
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- CN113999542A CN113999542A CN202111182878.8A CN202111182878A CN113999542A CN 113999542 A CN113999542 A CN 113999542A CN 202111182878 A CN202111182878 A CN 202111182878A CN 113999542 A CN113999542 A CN 113999542A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/008—Preparations of disperse dyes or solvent dyes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0097—Dye preparations of special physical nature; Tablets, films, extrusion, microcapsules, sheets, pads, bags with dyes
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Abstract
The invention provides a nano composite preparation of disperse dye and a preparation method thereof. The invention provides a nano composite preparation of a disperse dye, wherein the composite preparation comprises the disperse dye, a surfactant and a metal organic porous framework compound, and the disperse dye is loaded in the metal organic porous framework compound. The invention also provides a preparation method of the nano composite preparation of the disperse dye, which comprises the following steps: 1) preparing a mixed solution of disperse dye, surfactant and water; 2) adding metal ion salt and organic ligand into the mixed solution obtained in the step 1), stirring and mixing, carrying out coprecipitation reaction, centrifuging, washing and drying to obtain the nano composite preparation of the disperse dye. The preparation method of the disperse dye nano composite preparation does not need grinding equipment, high-pressure homogenizing equipment or a supergravity rotating packed bed, has low requirement on equipment, and reduces the energy consumption of production.
Description
Technical Field
The invention belongs to the technical field of dyes. In particular, the invention relates to a nano composite preparation of disperse dye, and also relates to a preparation method and application of the composite preparation.
Background
A disperse dye is a dye which is slightly soluble in water and is in a highly dispersed state in water by the action of a dispersant. With the increasing application requirements of terylene, the disperse dye industry is also developed rapidly. At present, the disperse dye is mainly applied to dyeing and printing of polyester fibers, and textiles dyed by the disperse dye are bright in color and excellent in quality. However, the post-treatment requirement of the disperse dye is relatively high, and the disperse dye is usually ground by a grinder or homogenized under high pressure in the presence of a large amount of dispersant to be in a highly dispersed state, so that the disperse dye can be used after stable crystal form particles are obtained.
The nano material has special interface effect, size effect, macroscopic quantum tunnel effect and the like, exerts new and different characteristics in the aspects of optical, acoustic, electric, magnetic, thermal and other properties, and is widely concerned by research in various fields. The disperse dye is prepared into the nano preparation in a modification mode, so that the dispersibility of the disperse dye in water can be effectively improved, and the operability of the disperse dye in the printing and dyeing process is improved.
The Chinese patent application with the application number of CN200610049968.9 discloses a process for preparing a nano-scale disperse blue 2BLN dye by a reprecipitation-homogenization method, which comprises the steps of firstly carrying out ball milling on a disperse blue 2BLN dye filter cake, an organic solvent and a dispersing agent to obtain an emulsion, then slowly dripping the emulsion into a dispersing agent aqueous solution which is strongly ground in a ball milling medium, and carrying out high-pressure homogenization treatment on the disperse dye solution after strong ball milling to obtain the nano-scale disperse blue 2BLN liquid dye. The average grain diameter of the dye liquid obtained by the process is 70nm, and the stability of the dye liquid is not changed after the dye liquid is placed for 2 months at normal temperature. However, the process needs to be subjected to multiple times of grinding and high-pressure homogenization, the process steps are complicated, the production energy consumption is high, the production cost is increased, and in addition, an organic solvent is also used in the preparation process, so that the environment is polluted.
Chinese patent application with application number CN201810471552.9 discloses a preparation method of nano disperse dye, which comprises the steps of dissolving the disperse dye in an organic solvent, filtering to remove impurities to obtain an organic solution containing the disperse dye, and marking as feed liquid A; dissolving a dispersant in water to obtain an aqueous solution containing the dispersant, and marking as feed liquid B; fully mixing and precipitating the feed liquid A and the feed liquid B by adopting a supergravity rotating packed bed to obtain nano disperse dye slurry; removing the organic solvent to prepare the nano disperse dye. The nano disperse dye prepared by the method has the particle size of less than 280nm, uniform particle size distribution and good dispersibility. However, this method requires the use of a supergravity rotating packed bed, has a high requirement for equipment, and requires the use of a large amount of organic solvent, which is likely to cause environmental pollution, and has severe conditions required for industrial production.
Metal-Organic frameworks (MOFs) are a porous crystalline material with ultrahigh porosity and large internal specific surface area, and are receiving intense attention from researchers in various fields. The metal organic framework material constructs a coordination polymer with a periodic regular network structure through self-assembly of an organic ligand and metal ions. The metal organic framework material has the characteristics of large specific surface area, high porosity, adjustable structure, simplicity in preparation, good chemical stability and the like, and plays an important role in the fields of gas storage, chemical separation, catalysis, energy storage, drug delivery and the like.
However, no studies have been made in the prior art concerning the relevance of metal-organic framework materials and disperse dyes. And the existing preparation method of the disperse dye is simple, good in stability and low in organic solvent consumption.
Disclosure of Invention
Based on the deficiencies of the prior art, it is an object of the present invention to provide a nanocomposite formulation of a disperse dye. Compared with the prior art, the preparation method of the disperse dye provided by the invention is simple, no additional organic solvent or mechanical equipment is needed, the production of large-batch nano-scale disperse dyes is facilitated, and the nano-composite preparation obtained by the method has better performances of water washing resistance, friction resistance, sunlight resistance and the like.
The purpose of the invention is realized by the following technical scheme:
in one aspect, the present invention provides a nanocomposite formulation of a disperse dye, wherein the composite formulation comprises a disperse dye, a surfactant, and a metal-organic porous skeleton compound, the disperse dye being supported in the metal-organic porous skeleton compound.
The nano composite preparation according to the present invention, wherein the surfactant is selected from polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, and mixtures thereof,
F-127、
F-68, Tween-80, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, and calcium lignosulfonate.
The nanocomposite formulation according to the present invention, wherein the disperse dye is selected from a disperse orange dye, a disperse blue dye, a disperse yellow dye, a disperse red dye, a disperse black dye, a disperse green dye, or a disperse violet dye; preferably, the disperse dye is disperse blue 2BLN, disperse yellow 5GL, disperse yellow brown 2BLS, disperse brilliant blue 2BLS, disperse navy S-2GL, disperse blue RRL, disperse pink R3L or disperse red 3B.
Preferably, the disperse dye comprises raw materials of the disperse dye and auxiliary agents; more preferably, the adjuvant is selected from one or more of lignin, anti-settling agents, anti-dust agents and/or dispersants.
The nanocomposite formulation according to the present invention, wherein the metal-organic porous skeleton compound is formed by self-assembly of metal ions and organic ligands.
Preferably, the metal ions are selected from one or more of zinc ions, copper ions, ferrous ions, and cobalt ions.
Preferably, the organic ligand is selected from one or more of 2-methylimidazole, 2-imidazolecarboxaldehyde, imidazole and benzimidazole.
Preferably, a modifier is also used in the formation of the metal organic porous framework compound; more preferably, the modifier is selected from one or more of imidazole-4, 5-dicarboxylic acid, 4-hydroxymethyl imidazole, imidazole-4-carboxylic acid methyl ester, imidazole-4-carboxylic acid ethyl ester, and 4-imidazole carboxylic acid.
The nanocomposite preparation according to the present invention, wherein the metal-organic porous skeleton compound is a metal-organic mesoporous skeleton compound; the aperture of the mesopores is 2-50 nm, preferably 3-10 nm. The inventors of the present invention found that the larger the mesopores of the metal-organic mesoporous framework compound, the more advantageous the preparation and subsequent use of the nanocomposite preparation of the disperse dye of the present application.
Preferably, the metal organic mesoporous framework compound is Zn-ZIF (ZIF-8, ZIF-11, ZIF-64, ZIF-90, etc.), Cu-ZIF, Fe-ZIF, Co-ZIF (ZIF-9, ZIF-67, etc.).
More preferably, the metal organic mesoporous framework compound is ZIF-8, which is generated by coprecipitation of zinc ions and 2-methylimidazole.
Wherein ZIF-8 is formed by zinc ions and 2-methylimidazole, ZIF-11 is formed by zinc ions and benzimidazole, ZIF-64 is formed by zinc ions and imidazole, ZIF-90 is formed by zinc ions and 2-imidazolecarboxaldehyde, ZIF-9 is formed by cobalt ions and benzimidazole, and ZIF-67 is formed by cobalt ions and 2-methylimidazole.
The nano composite preparation is characterized in that the mass ratio of the disperse dye to the metal organic porous skeleton compound is 20: 1-1: 20; preferably 10:1 to 1: 10; more preferably 10: 1-1: 1; further preferably 2: 1 to 5: 1.
The mass ratio of the disperse dye to the surfactant is 50: 1-5: 1; preferably 20:1 to 10: 1. The invention also provides a preparation method of the nano composite preparation of the disperse dye, which comprises the following steps:
1) preparing a mixed solution of disperse dye, surfactant and water;
2) adding metal ion salt and organic ligand into the mixed solution obtained in the step 1), stirring and mixing, carrying out coprecipitation reaction, centrifuging, washing and drying to obtain the nano composite preparation of the disperse dye.
According to the method of the invention, in the step 1), the concentration of the disperse dye in the mixed solution of the disperse dye, the surfactant and the water is 1-1000mg/mL, preferably 5-200mg/mL, more preferably 5-100mg/mL, and further preferably 10-50 mg/mL.
Preferably, in step 1), the surfactant is selected from polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, or polyethylene glycol, or polyethylene glycol, or polyethylene glycol, or polyethylene glycol, or polyethylene glycol,
F-127、
F-68, Tween-80, one or more of sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, calcium lignosulfonate; preferably, the concentration of the surfactant is 0.1-100mg/mL, preferably 0.5-50mg/mL, more preferably 0.5-10mg/mL, and even more preferably 1-5 mg/mL. In the invention, the disperse dye is firstly modified by using the surfactant, the modified disperse dye has improved dispersibility in an aqueous solution, and can be loaded in a metal organic porous framework compound in a form of smaller particle size.
The method according to the invention, wherein in step 2), the metal ions are selected from one or more of zinc ions, copper ions, ferrous ions and cobalt ions; preferably, the concentration of the metal ions in the mixed solution is 0.1-100mg/mL, preferably 0.5-50mg/mL, and more preferably 0.5-10 mg/mL.
According to the method, in the step 2), the organic ligand is selected from one or more of 2-methylimidazole, 2-imidazole formaldehyde, imidazole and benzimidazole; preferably, the concentration of the organic ligand is 1-1000mg/mL, preferably 5-200mg/mL, more preferably 5-100mg/mL, and even more preferably 10-50 mg/mL.
According to the method, in the step 2), a modifier is also added, wherein the modifier is selected from one or more of 4-imidazole carboxylic acid, 4-hydroxymethyl imidazole, imidazole-4-methyl formate, imidazole-4-ethyl formate and imidazole-4, 5-dicarboxylic acid; preferably, the concentration of the modifying agent in the aqueous solution is 0.1-100mg/mL, preferably 0.1-50mg/mL, more preferably 0.1-10 mg/mL. The inventor of the invention finds that the modifier can enable a large amount of mesopores to be generated inside the metal organic framework, so that the disperse dye-mesoporous metal organic framework nano composite preparation can quickly release the disperse dye in the printing and dyeing process, and the effect of level dyeing is achieved.
The method according to the invention, wherein a stirring step is included in the preparation of step 1) and step 2), respectively; preferably, the stirring time is 10min-24 h;
preferably, the reaction temperature of step 1) and step 2) is room temperature.
The method according to the invention, wherein in the step 2), the rotation speed of the centrifugation is 3000-12000rpm, the centrifugation time is 1-30min, and the drying mode is at least one selected from natural air drying, freeze drying and spray drying.
Compared with the prior art, the invention has the following advantages:
1. the preparation method of the disperse dye nano composite preparation does not need grinding equipment, high-pressure homogenizing equipment or a supergravity rotating packed bed, has low requirement on equipment, and reduces the energy consumption of production.
2. The preparation method of the disperse dye nano composite preparation only needs to be carried out at normal temperature and normal pressure, and does not need to use any additional organic solvent, thereby reducing the pollution of the production process to the environment.
3. The preparation method of the disperse dye nano composite preparation has certain universality, is almost suitable for all disperse dyes, has low production cost, and can be continuously operated on line.
4. The nano composite preparation of the disperse dye provided by the method has better dispersibility in aqueous solution than the existing disperse dye, and has better performances of water washing resistance, friction resistance, sunlight resistance and the like. In addition, the nano composite preparation of the disperse dye can quickly release the disperse dye in the printing and dyeing process, so that the effect of level dyeing is achieved, and the content of the disperse dye in eluent is reduced.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments of the present invention will be briefly described below, and it is obvious that the drawings described below are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a transmission electron micrograph of a disperse blue 2BLN nanocomposite formulation prepared according to example 4 of the present invention;
fig. 2 is a particle size dispersion profile of a disperse blue 2BLN nanocomposite formulation prepared according to example 4 of the present invention in an aqueous solution.
Detailed Description
Features and exemplary embodiments of various aspects of the present invention will be described in detail below. In the following detailed description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. It will be apparent, however, to one skilled in the art that the present invention may be practiced without some of these specific details. The following description of the embodiments is merely intended to provide a better understanding of the present invention by illustrating examples of the present invention.
The invention provides a preparation method of a novel nano composite preparation, which comprises the steps of synthesizing a nano composite preparation by a one-step coprecipitation method of disperse dye molecules, a surfactant, metal ions, an organic ligand and a modifier in an aqueous solution, embedding the disperse dye molecules in nano particles, and then obtaining the disperse dye-mesoporous metal organic framework nano composite preparation through the processes of centrifugation, washing, drying and the like. By the embedding method, the dispersibility of the disperse dye in water is effectively improved, and the performances of washing resistance, friction resistance, sunlight resistance and the like of the dye are improved. In addition, the disperse dye-mesoporous metal organic framework nano composite preparation provided by the invention has the advantages of lower preparation cost and use cost, less pollutants and convenience in transportation and storage.
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples.
Example 1 preparation of nanocomposite formulations using the method of the invention
1) 10g of disperse blue 2BLN (purchased from Shanyu group, Zhejiang) and 2g of polyvinyl alcohol were weighed into 1L of water, and stirred and mixed at room temperature for 1 hour to obtain a mixture.
2) And sequentially adding 18g of 2-methylimidazole, 2g of zinc nitrate and 2g of 4-imidazolecarboxylic acid into the mixed solution, stirring and mixing for 2 hours at room temperature, centrifuging and washing for 3 times, wherein the rotating speed of centrifugation is 8000rpm, the centrifugation time of each time is 5min, and naturally drying to obtain the disperse blue 2 BLN-mesoporous metal organic framework nano composite preparation.
The aperture of the porous material is 2.8nm as determined by a nitrogen adsorption and desorption instrument. The particle size of the particle dispersed in the water solution is 119nm by a Malvern nanometer particle size analyzer test. The result shows that the disperse blue 2 BLN-mesoporous metal organic framework nano composite preparation has better dispersibility in aqueous solution and is not easy to generate agglomeration.
Example 2 preparation of nanocomposite formulations using the method of the invention
1) 20g of disperse blue 2BLN and 2g of polyvinylpyrrolidone are weighed into 1L of water, and stirred and mixed for 1 hour at room temperature to obtain a mixed solution.
2) And sequentially adding 20g of 2-methylimidazole, 1.5g of cobalt chloride and 1.5g of 4-hydroxymethylimidazole into the mixed solution, stirring and mixing for 4 hours at room temperature, centrifuging and washing for 3 times, wherein the centrifugal rotation speed is 8000rpm, the centrifugation time is 5min each time, and naturally drying to obtain the disperse blue 2 BLN-mesoporous metal organic framework nano composite preparation.
The aperture of the porous material is 3.2nm as determined by a nitrogen adsorption and desorption instrument. The particle size of the particle dispersed in the water solution is 146nm by a Malvern nanometer particle size analyzer test. The result shows that the disperse blue 2 BLN-mesoporous metal organic framework nano composite preparation has better dispersibility in aqueous solution and is not easy to generate agglomeration.
Example 3 preparation of nanocomposite formulations using the method of the invention
1) 10g of disperse yellow 5GL (purchased from Shanyu group, Zhejiang) and 2g of polyvinyl alcohol were weighed into 1L of water, and stirred and mixed at room temperature for 1 hour to obtain a mixed solution.
2) And sequentially adding 18g of 2-methylimidazole, 2g of zinc nitrate and 2g of 4-imidazolecarboxylic acid into the mixed solution, stirring and mixing for 2 hours at room temperature, centrifuging and washing for 3 times, wherein the rotating speed of centrifugation is 8000rpm, the centrifugation time of each time is 5min, and naturally drying to obtain the disperse yellow 5 GL-mesoporous metal organic framework nano composite preparation.
The aperture of the porous material is 3.3nm as determined by a nitrogen adsorption and desorption instrument. The particle size of the product dispersed in water solution is 176nm by Malvern nanometer particle size analyzer test. The result shows that the disperse yellow 5 GL-mesoporous metal organic framework nano composite preparation has better dispersibility in aqueous solution and is not easy to agglomerate.
Example 4 preparation of nanocomposite formulations using the method of the invention
1) 500g of disperse blue 2BLN and 100g of polyvinyl alcohol were weighed out and added to 50L of water, and stirred and mixed at room temperature for 1 hour to obtain a mixed solution.
2) Adding 900g of 2-methylimidazole, 100g of zinc nitrate and 100g of 4-imidazolecarboxylic acid into the mixed solution in sequence, stirring and mixing for 6 hours at room temperature, centrifuging and washing for 3 times, wherein the rotating speed of the centrifugation is 8000rpm, the centrifugation time of each time is 10min, and performing spray drying to obtain the disperse blue 2 BLN-mesoporous metal organic framework nano composite preparation.
The results are shown in fig. 1 and fig. 2, wherein fig. 1 is a transmission electron micrograph of the dispersed blue 2BLN nanocomposite formulation; fig. 2 is a distribution diagram of the particle size dispersion of the disperse blue 2BLN nanocomposite formulation in aqueous solution.
The aperture of the porous material is 3.5nm as determined by a nitrogen adsorption and desorption instrument. The particle size of the product dispersed in water solution is 220nm by Malvern nanometer particle size analyzer test. The result shows that the disperse blue 2 BLN-mesoporous metal organic framework nano composite preparation has better dispersibility in aqueous solution and is not easy to generate agglomeration.
Example 5 preparation of nanocomposite formulations using the method of the invention
1) 20g of disperse blue 2BLN (purchased from Shanyu group, Zhejiang) and 0.4g of calcium lignosulfonate were weighed into 1L of water, and stirred and mixed at room temperature for 24 hours to obtain a mixed solution.
2) Adding 2-imidazole formaldehyde 0.9g, copper nitrate 0.1g and imidazole-4, 5-dicarboxylic acid 0.2g into the mixed solution in sequence, stirring and mixing for 10min at room temperature, centrifuging and washing for 3 times, wherein the rotating speed of centrifugation is 3000rpm, the centrifugation time of each time is 30min, and naturally drying to obtain the disperse blue 2 BLN-mesoporous metal organic framework nano composite preparation.
The aperture of the porous material is 2.5nm as determined by a nitrogen adsorption and desorption instrument. The particle size of the product dispersed in water solution is 131nm by Malvern nanometer particle size analyzer test. The result shows that the disperse blue 2 BLN-mesoporous metal organic framework nano composite preparation has better dispersibility in aqueous solution and is not easy to generate agglomeration.
Example 6 preparation of nanocomposite formulations using the method of the invention
1) 1g of disperse blue 2BLN (purchased from Shanyu group, Zhejiang) and 0.2g of polyethylene glycol were weighed into 1L of water, and stirred and mixed at room temperature for 1 hour to obtain a mixture.
2) And sequentially adding 18g of imidazole, 2g of ferrous nitrate and 1g of imidazole-4-methyl formate into the mixed solution, stirring and mixing at room temperature for 2 hours, centrifuging and washing for 3 times, wherein the centrifugal rotation speed is 8000rpm, the centrifugal time is 5min each time, and naturally drying to obtain the disperse blue 2 BLN-mesoporous metal organic framework nano composite preparation.
The aperture of the porous material is 3.7nm as determined by a nitrogen adsorption and desorption instrument. The particle size of the particle dispersed in the water solution is 217nm by the test of a Malvern nanometer particle size analyzer. The result shows that the disperse blue 2 BLN-mesoporous metal organic framework nano composite preparation has better dispersibility in aqueous solution and is not easy to generate agglomeration.
Example 7 preparation of nanocomposite formulations using the method of the invention
1) 20g of disperse blue 2BLN (purchased from Shanyu group, Zhejiang) and 1g of disperse blue are weighed out
F-127 is added into 1L of water, stirred and mixed for 1h at room temperature to obtain a mixed solution.
2) And sequentially adding 9g of benzimidazole, 1g of cobalt nitrate and 1g of imidazole-4-ethyl formate into the mixed solution, stirring and mixing at room temperature for 2 hours, centrifuging and washing for 3 times, wherein the rotating speed of centrifugation is 8000rpm, the centrifugation time of each time is 5min, and naturally drying to obtain the disperse blue 2 BLN-mesoporous metal organic framework nano composite preparation.
The aperture of the porous material is 3.2nm as determined by a nitrogen adsorption and desorption instrument. The particle size of the product dispersed in water solution is 195nm as tested by Malvern nanometer particle size analyzer. The result shows that the disperse blue 2 BLN-mesoporous metal organic framework nano composite preparation has better dispersibility in aqueous solution and is not easy to generate agglomeration.
Example 8 Using the inventionMethod for preparing nano composite preparation
1) 50g of disperse blue 2BLN (purchased from Shanyu group Co., Ltd., Zhejiang) and 5g of Tween-80 were weighed out and added to 1L of water, and the mixture was stirred and mixed at room temperature for 1 hour to obtain a mixture.
2) And sequentially adding 9g of 2-methylimidazole, 1g of zinc nitrate and 1g of 4-imidazolecarboxylic acid into the mixed solution, stirring and mixing for 2 hours at room temperature, centrifuging and washing for 3 times, wherein the rotating speed of centrifugation is 8000rpm, the centrifugation time of each time is 5min, and naturally drying to obtain the disperse blue 2 BLN-mesoporous metal organic framework nano composite preparation.
The aperture of the porous material is 2.9nm as determined by a nitrogen adsorption and desorption instrument. The particle size of the product dispersed in water solution is 183nm by Malvern nanometer particle size analyzer test. The result shows that the disperse blue 2 BLN-mesoporous metal organic framework nano composite preparation has better dispersibility in aqueous solution and is not easy to generate agglomeration.
Comparative example 1
Weighing 10g of disperse blue 2BLN (purchased from Shanyu group Co., Ltd., Zhejiang province), 18g of 2-methylimidazole, 2g of zinc nitrate and 2g of 4-imidazolecarboxylic acid, sequentially adding into 1L of the aqueous solution, stirring and mixing at room temperature for 2h, centrifuging and washing for 3 times, wherein the rotation speed of centrifugation is 8000rpm, the centrifugation time of each time is 5min, and naturally drying to obtain the disperse blue 2 BLN-metal organic framework composite preparation.
The particle size of the particles dispersed in the aqueous solution is 5.4 μm by a Malvern nanometer particle size analyzer test. The result shows that if the disperse blue 2BLN is not modified by using a surfactant, the disperse blue 2BLN is easy to agglomerate in an aqueous solution, and the particle size of the composite preparation is larger and the phenomenon of agglomeration and sedimentation is easy to occur after the composite preparation is loaded on a metal organic framework.
Comparative example 2
10g of disperse blue 2BLN (purchased from Shanyu group, Zhejiang) and 2g of polyvinyl alcohol were weighed into 1L of water, and stirred and mixed at room temperature for 1 hour to obtain a mixture. And adding the mixed solution into a sand mill, grinding for 3h, and naturally drying the treatment solution to obtain the disperse blue 2BLN preparation. The particle size of the particles dispersed in the aqueous solution was 3.7 μm as measured by a Malvern nanometer particle sizer. The results show that if the process of grinding by using a sand mill is used, the particle size of the disperse blue 2BLN is larger, the phenomenon of agglomeration and sedimentation is easy to occur, and the energy consumption of the grinding process is higher.
Comparative example 3
10g of disperse blue 2BLN (purchased from Shanyu group, Zhejiang) and 2g of polyvinyl alcohol were weighed into 1L of water, and stirred and mixed at room temperature for 1 hour to obtain a mixture. And (3) adding the mixed solution into a high-pressure homogenizer, circulating for 3 times, wherein the homogenizing pressure is 1000bar, and naturally drying the treated solution to obtain the disperse blue 2BLN preparation. The particle size of the particles dispersed in the aqueous solution is 1.5 μm by a Malvern nanometer particle size analyzer test. The result shows that if a high-pressure homogenization process is used, the particle size of the disperse blue 2BLN is still larger, and the phenomenon of agglomeration and sedimentation is easy to occur.
While the invention has been described with reference to specific embodiments, the invention is not limited thereto, and various equivalent modifications and substitutions can be easily made by those skilled in the art within the technical scope of the invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. A nanocomposite formulation of a disperse dye, characterized in that the composite formulation comprises a disperse dye, a surfactant and a metal-organic porous framework compound, and the disperse dye is supported in the metal-organic porous framework compound.
2. The nanocomposite formulation according to claim 1, wherein said surfactant is selected from polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol,
F-127、
F-68, Tween-80, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, and woodOne or more of calcium lignosulphonates.
3. The nanocomposite formulation according to claim 1 or 2, wherein the disperse dye is selected from disperse orange dye, disperse blue dye, disperse yellow dye, disperse red dye, disperse black dye, disperse green dye or disperse violet dye; the disperse dye is preferably disperse blue 2BLN, disperse yellow 5GL, disperse yellow brown 2BLS, disperse brilliant blue 2BLS, disperse navy S-2GL, disperse blue RRL, disperse pink R3L or disperse red 3B;
preferably, the disperse dye comprises raw materials of the disperse dye and auxiliary agents; more preferably, the adjuvant is selected from one or more of lignin, anti-settling agents, anti-dust agents and/or dispersants.
4. The nanocomposite formulation according to any one of claims 1 to 3, wherein the metal-organic porous framework compound is formed by self-assembly of metal ions and organic ligands;
preferably, the metal ions are selected from one or more of zinc ions, copper ions, ferrous ions and cobalt ions;
preferably, the organic ligand is selected from one or more of 2-methylimidazole, 2-imidazolecarboxaldehyde, imidazole and benzimidazole;
preferably, a modifier is also used in the formation of the metal organic porous framework compound;
more preferably, the modifier is selected from one or more of imidazole-4, 5-dicarboxylic acid, 4-hydroxymethyl imidazole, imidazole-4-carboxylic acid methyl ester, imidazole-4-carboxylic acid ethyl ester, and 4-imidazole carboxylic acid.
5. The nanocomposite formulation according to any one of claims 1 to 4, wherein the metal-organic porous framework compound is a metal-organic mesoporous framework compound; the aperture of the mesopores is 2-50 nm, preferably 3-10 nm;
preferably, the metal organic mesoporous framework compound is Zn-ZIF, Cu-ZIF, Fe-ZIF or Co-ZIF;
more preferably, the Zn-ZIF is IF-8, ZIF-11, ZIF-64 or ZIF-90; the Co-ZIF is ZIF-9 or ZIF-67.
6. The nanocomposite formulation according to any one of claims 1 to 5, wherein the mass ratio of the disperse dye to the metal-organic porous skeleton compound is 20:1 to 1: 20; preferably 10:1 to 1: 10; more preferably 10:1 to 1: 1; further preferably 2: 1-5: 1; and/or
The mass ratio of the disperse dye to the surfactant is 50: 1-5: 1; preferably 20:1 to 10: 1.
7. A method of preparing a nanocomposite formulation of a disperse dye according to any one of claims 1 to 6, the method comprising the steps of:
1) preparing a mixed solution of disperse dye, surfactant and water;
2) adding metal ion salt and organic ligand into the mixed solution obtained in the step 1), stirring and mixing, carrying out coprecipitation reaction, centrifuging, washing and drying to obtain the nano composite preparation of the disperse dye.
8. The method according to claim 7, wherein in the step 1), the concentration of the disperse dye in the mixed solution of the disperse dye, the surfactant and the water is 1-1000mg/mL, preferably 5-200mg/mL, more preferably 5-100mg/mL, and further preferably 10-50 mg/mL; and/or the concentration of the surfactant is 0.1-100mg/mL, preferably 0.5-50mg/mL, more preferably 0.5-10mg/mL, and still more preferably 1-5 mg/mL.
9. The method according to claim 7 or 8, wherein in step 2), the concentration of metal ions in the mixed solution is 0.1-100mg/mL, preferably 0.5-50mg/mL, more preferably 0.5-10 mg/mL; and/or the concentration of the organic ligand is 1-1000mg/mL, preferably 5-200mg/mL, more preferably 5-100mg/mL, and further preferably 10-50 mg/mL;
and/or, in step 2), a modifier is also added; preferably, the concentration of the modifying agent in the aqueous solution is 0.1-100mg/mL, preferably 0.1-50mg/mL, more preferably 0.1-10 mg/mL.
10. The method according to any one of claims 7 to 9, wherein a step of stirring is included in the preparation of step 1) and step 2), respectively; preferably, the stirring time is 10min-24 h;
preferably, the reaction temperature of step 1) and step 2) is room temperature;
more preferably, in step 2), the rotation speed of the centrifugation is 3000-12000rpm, the centrifugation time is 1-30min, and the drying manner is selected from at least one of natural air drying, freeze drying and spray drying.
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| CN113121834A (en) * | 2019-12-31 | 2021-07-16 | 中国石油化工股份有限公司 | Composite metal organic framework material and preparation method thereof |
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| WO2017078609A1 (en) * | 2015-11-05 | 2017-05-11 | Su Holding Ab | One-pot synthesis of metal-organic frameworks with encapsulated target-molecule and their use |
| CN110499043A (en) * | 2018-05-17 | 2019-11-26 | 北京化工大学 | A kind of preparation method of nano-dispersed dyestuff |
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| CN114773878B (en) * | 2022-04-29 | 2022-10-11 | 浙江博澳新材料股份有限公司 | High-dispersity nano disperse dye and preparation method thereof |
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