CN110698882A - Preparation method of colored nanosphere colorant - Google Patents
Preparation method of colored nanosphere colorant Download PDFInfo
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- CN110698882A CN110698882A CN201910976987.3A CN201910976987A CN110698882A CN 110698882 A CN110698882 A CN 110698882A CN 201910976987 A CN201910976987 A CN 201910976987A CN 110698882 A CN110698882 A CN 110698882A
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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
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/28—Compounds of silicon
- C09C1/30—Silicic acid
- C09C1/309—Combinations of treatments provided for in groups C09C1/3009 - C09C1/3081
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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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/28—Compounds of silicon
- C09C1/30—Silicic acid
- C09C1/3063—Treatment with low-molecular organic compounds
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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
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
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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
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/673—Inorganic compounds
- D06P1/67383—Inorganic compounds containing silicon
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Coloring (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
The invention discloses a preparation method of a colored nanosphere colorant, which is carried out according to the following steps in sequence: firstly, adding nanospheres into a solvent, and then carrying out ultrasonic dispersion until uniform sol solution is obtained; magnetically stirring the sol solution, keeping the sol solution in a constant-temperature bath at 5-100 ℃, adding a color development matrix, and adding a reaction regulator; thirdly, reacting the reaction solution added with the reaction regulator for a period of time at the temperature of 5-100 ℃; fourthly, centrifugally separating the liquid after the reaction in the third step to obtain a crude product; fifthly, washing the crude product by water and an organic solvent; sixthly, drying the washed crude product to obtain the colored nanosphere colorant. The invention introduces a series of conjugated structure systems on the surfaces of the nanospheres through a synthesis reaction to generate chemical bonds, so that the modified nanospheres have full-color-spectrum colors, are used as a universal colorant, and are suitable for coloring paper pulp and ink and different fiber materials.
Description
Technical Field
The invention belongs to the technical field of coloring agent preparation, and relates to a preparation method of a nanometer coloring agent, in particular to a preparation method of a colored nanosphere coloring agent.
Background
In the prior art, different dyes are selected according to different fiber varieties and specifications for coloring textile fibers, and a special dyeing process is formulated to meet the requirements of specific colors on different fibers, so that higher requirements are provided for dye synthesis. However, in the process of dyeing cotton fibers by using the reactive dye, the problems of low fixation rate, easy hydrolysis of the dye, poor stability, serious environmental pollution caused by ineffective decomposition and the like exist.
The application of nano materials in the textile field is extensive and deep. The nano material has small size effect, surface effect, macroscopic quantum tunneling effect and quantum size effect. After the material is subdivided into nanometer levels, the optical, thermal, electrical, magnetic, mechanical and chemical properties of the material are obviously different from those of a bulk object. Among them, metal oxides represented by spherical nano-silica, titanium dioxide, zinc oxide, etc. have high practical value in functional textiles. Due to the surface effect, the spherical nanoparticles can realize efficient and stable adsorption on the fiber material.
Taking nano-silica as an example, as white powder with a white sphere presenting a net three-dimensional structure, the surface of the nano-silica sphere contains hydroxyl groups in different states and has certain reactivity. The preparation method of the nano silicon dioxide spheres is various and mainly comprises a calcination method, a gas phase method, a sol-gel method, a precipitation method and the like. The nano silicon dioxide spheres prepared by different methods have different properties. To introduce specific properties, they may be surface modified, including in situ modification methods and graft modification methods.
The nanometer silica ball and dye matrix with certain activity react chemically in the presence of catalyst to introduce the color body to the surface of the silica ball to obtain the color nanometer ball. At present, the research on the nanosphere composite functionalized fiber material is more, but the research on the preparation of the colored nanosphere and the coloring of the textile material is rarely reported.
Disclosure of Invention
The invention aims to provide a preparation method of a colored nanosphere colorant, which can obtain a full-color-spectrum nano-scale colorant through a series of reactions, has simple and easy synthetic method, can be used for dyeing textile materials, can be dispersed in a water system, has simple dyeing process and has no selectivity.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing a colored nanosphere colorant, characterized by comprising the following steps in sequence:
firstly, adding nanospheres with active groups into a solvent, and then carrying out ultrasonic dispersion until a uniform sol solution A is obtained;
magnetically stirring the sol solution A, keeping the sol solution in a constant-temperature bath at 5-100 ℃, adding a color development matrix, and adding a reaction regulator to prepare a reaction solution B;
thirdly, reacting the reaction liquid B for 3-8 hours at the temperature of 5-100 ℃ to obtain a liquid C;
fourthly, carrying out centrifugal separation on the liquid C to obtain a crude product D;
fifthly, washing the crude product D to obtain a substance E;
and sixthly, drying the substance E to obtain the colored nanosphere colorant.
By way of limitation, the nanospheres with active groups used in the first step are nanospheres with active groups prepared by, but not limited to, calcination, vapor phase, sol-gel method or precipitation method.
As a second limitation, the nanosphere with active group in the first step is made of zero-dimensional nanomaterial.
As a third limitation, the nanospheres with active groups in step one include, but are not limited to, silica nanospheres, titanium dioxide nanospheres, zinc oxide nanospheres, zirconium oxide nanospheres, or football alkene nanospheres.
As a fourth limitation, the solvent in the first step is any one of water, ethanol, DMF and toluene.
As a fifth limitation, the reaction modifier in step two is sodium carbonate or an organic base.
As a sixth limitation, in the fifth step, the washing process is to wash with water and then with an organic solvent.
As a seventh limitation, in the fifth step, the washing process is to wash with the organic solvent and then with water.
As an eighth limitation, in step five, the wash is performed until the residual liquid is colorless, and the absorbance value measured by a spectrophotometer is 0.
As a ninth limitation, the drying temperature in the sixth step is 60 to 100 ℃.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the technical progress that:
(1) by adopting the method provided by the invention, a series of color bodies are selected to graft and modify the nanospheres, so that the full-color spectrum nano colorant can be obtained, and the colorant has no selectivity and is a universal colorant; the adsorption performance test result shows that the dye has good colorability on both natural fibers and synthetic fibers, so that the dye synthesis process is greatly simplified, and a large amount of complicated dye synthesis work is avoided;
(2) different from the traditional colorant, the colorant prepared by the method is suitable for coloring paper pulp, ink and different fiber materials, is not specific to a certain fiber material, has a good coloring effect on most common textile fiber materials, and can introduce a certain functional effect;
(3) the synthesis method used in the invention is simple and easy to implement, and the dyeing process is simple and convenient to operate, and has high application value.
The invention is applicable to the technical field of colorant preparation.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.
In the drawings:
FIG. 1 is a SEM photograph of the silica nanospheres prepared in step one of example 1 of the present invention;
FIG. 2 is an enlarged view of a portion of FIG. 1;
FIG. 3 is a SEM photograph of red powdered nanosphere colorant obtained in step seven of example 1 of the present invention;
fig. 4 is a partially enlarged view of fig. 3.
Detailed Description
Preferred embodiments of the present invention will be described below with reference to the accompanying drawings. It should be understood that the preferred embodiments described herein are for purposes of illustration and explanation only and are not intended to limit the present invention.
Example 1 a method of making a colored nanosphere colorant
The manufacturing process of this embodiment is performed according to the following sequence of steps:
firstly, preparing nanospheres with active groups on the surfaces by a sol-gel method;
secondly, containing 0.7g of nanospheres, adding 70ml of deionized water into the weighed nanospheres as a solvent to enable the bath ratio to be =100:1, and then carrying out ultrasonic dispersion for a time t1=20min to obtain a uniform sol solution a;
thirdly, magnetically stirring the sol solution A, and then keeping the temperature at T1=75 ℃, adding 0.028G of commercial dye reactive brilliant red K-2G (4%, o.w.f) as a color development matrix, and then adding sodium carbonate as a reaction regulator to obtain a reaction solution B;
fourthly, the reaction liquid B is heated to T2Reaction at 75 ℃ for t2=5h, liquid C was prepared;
fifthly, carrying out centrifugal separation on the liquid C to obtain a crude product D;
sixthly, washing the crude product D with water and an organic solvent in sequence to obtain a substance E, wherein when the washing result is that the residual liquid is colorless, the absorbance value measured by a spectrophotometer is 0;
seventhly, the substance E is heated at the temperature T3Vacuum drying at 70 deg.C to obtain red nanosphere colorant.
Wherein, the bath ratio in the second step refers to the ratio of the emulsion mass to the nanospheres mass. In the third step, the amount of the added reaction regulator needs to be controlled to adjust the pH value of the reaction system, so that the pH = 9-10, and the amount of the reaction regulator is 0-1 g.
Taking the nanosphere as an example of a silica nanosphere, as shown in fig. 1, it is a field emission scanning electron microscope photograph of the white powdery silica nanosphere prepared in step one, and as can be seen from fig. 1, the average particle size of the nanosphere is 50 nm. And (3) obtaining a red powdery nanosphere colorant after the reaction of the second step to the seventh step, wherein a field emission scanning electron microscope photo of the red powdery nanosphere colorant is shown in fig. 2, and as can be seen from fig. 2, the particle size of the red powdery nanosphere colorant is between 50nm and 80 nm.
The adsorption experiment of the red powdery nanosphere colorant and the cellulose fiber is carried out: 0.3 g/L of red nano-silica emulsion, the bath ratio is 100:1, at 80 ℃, when the adsorption time reaches 136 min, the adsorption quantity of the red nano-silica on the fabric does not increase along with the time extension any more, the adsorption balance is reached, and the maximum adsorption quantity when the maximum adsorption is reached is 28.9 mg/g. Thermodynamic parameters are calculated to find that: the adsorption of the red nano-silica on the cotton fabric is a process of delta G <0, delta H >0 and delta S >0, namely a process of spontaneous absorption, endothermic absorption and entropy value increase, and after the adsorption model is fitted, the adsorption process is found to be more consistent with a Langmuir (Langmuir) type adsorption model, the fitting variance is 0.9476, and the adsorption process can be considered as single-layer adsorption. After the adsorption kinetic parameters are calculated, the following results are found: the reaction number of the adsorption process is 1.45. The above adsorption data all indicate that the colorant is capable of achieving good coloration of the cellulose fibers.
Examples 2-9 a method of preparing a colored nanosphere colorant
The preparation of examples 2-9 was substantially the same as that of example 1, except that some of the technical parameters involved were different, as described in table 1 below:
table 1 technical parameter tables for examples 2-9
In the third step of examples 2 and 3, the amount of the reaction modifier is 0 to 0.8 g.
Examples 1-9, nanospheres in step one were also available directly from the purchase route. The types of nanospheres include, but are not limited to, silicon dioxide, titanium dioxide, zinc oxide, zirconium oxide, football alkene, and all nanospheres with active groups on their surfaces made of zero-dimensional nanomaterials. In practical use, the dye precursors in the third step can be selected according to actual needs, and examples 1 to 9 are only exemplified by the commercial dye reactive brilliant red K-2G.
In examples 1-9, nanospheres can also be prepared by calcination, vapor phase, precipitation, or other methods. The solvents of examples 3-9 were exchanged for toluene.
In the sixth step of examples 1 to 9, the washing process may be carried out by washing with an organic solvent and then with water.
Claims (10)
1. A method for preparing a colored nanosphere colorant, characterized by comprising the following steps in sequence:
firstly, adding nanospheres with active groups into a solvent, and then carrying out ultrasonic dispersion until a uniform sol solution A is obtained;
magnetically stirring the sol solution A, keeping the sol solution in a constant-temperature bath at 5-100 ℃, adding a color development matrix, and adding a reaction regulator to prepare a reaction solution B;
thirdly, reacting the reaction liquid B for 3-8 hours at the temperature of 5-100 ℃ to obtain a liquid C;
fourthly, carrying out centrifugal separation on the liquid C to obtain a crude product D;
fifthly, washing the crude product D to obtain a substance E;
and sixthly, drying the substance E to obtain the colored nanosphere colorant.
2. The method for preparing colored nanosphere colorant according to claim 1, wherein the nanospheres with active group used in step one are nanospheres with active group prepared by, but not limited to, calcining method, vapor phase method, sol-gel method or precipitation method.
3. The method for preparing colored nanosphere colorant according to claim 1 or 2, wherein the nanospheres with active group in step one are made of zero-dimensional nanomaterial.
4. The method for preparing a colored nanosphere colorant according to claim 1 or 2, wherein the nanospheres with active group in step one include but are not limited to silica nanospheres, titanium dioxide nanospheres, zinc oxide nanospheres, zirconium oxide nanospheres or football alkene nanospheres.
5. The method for preparing colored nanosphere colorant according to claim 1 or 2, wherein the solvent in step one is any one of water, ethanol, DMF and toluene.
6. The method for preparing a colored nanosphere colorant according to claim 1 or 2, wherein the reaction modifier in step two is sodium carbonate or organic base.
7. The method of claim 1 or 2, wherein in step five, the washing process is performed by washing with water and then with an organic solvent.
8. The method for preparing a colored nanosphere colorant according to claim 1 or 2, wherein in step five, the washing process comprises washing with organic solvent and then washing with water.
9. The method of claim 1 or 2, wherein in step five, the washing is performed until the residual liquid is colorless, and the absorbance value measured by a spectrophotometer is 0.
10. The method for preparing colored nanosphere colorant according to claim 1 or 2, wherein the drying temperature in the sixth step is 60-100 ℃.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN101538418A (en) * | 2009-04-16 | 2009-09-23 | 西安工程大学 | Acidic bright red/ZnO nuclear shell structure nanometer composite material and preparation method thereof |
| CN102234507A (en) * | 2010-05-05 | 2011-11-09 | 张永昶 | Preparation of fluorescent silicon dioxide nanospheres |
| CN107486112A (en) * | 2017-08-08 | 2017-12-19 | 浙江工商大学 | A kind of preparation method of the single dispersing colour silicon dioxide nanosphere of nondiscoloration |
| CN109486046A (en) * | 2018-10-31 | 2019-03-19 | 东华大学 | A kind of preparation method of disperse dyes/polystyrene/silica dioxide composite particles |
-
2019
- 2019-10-15 CN CN201910976987.3A patent/CN110698882A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3437921A1 (en) * | 1984-10-17 | 1986-04-17 | Peter 8000 München Weil | Agent and device especially for descaling domestic equipment |
| CN101538418A (en) * | 2009-04-16 | 2009-09-23 | 西安工程大学 | Acidic bright red/ZnO nuclear shell structure nanometer composite material and preparation method thereof |
| CN102234507A (en) * | 2010-05-05 | 2011-11-09 | 张永昶 | Preparation of fluorescent silicon dioxide nanospheres |
| CN107486112A (en) * | 2017-08-08 | 2017-12-19 | 浙江工商大学 | A kind of preparation method of the single dispersing colour silicon dioxide nanosphere of nondiscoloration |
| CN109486046A (en) * | 2018-10-31 | 2019-03-19 | 东华大学 | A kind of preparation method of disperse dyes/polystyrene/silica dioxide composite particles |
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| 姚小亭: "二氧化硅荧光纳米颗粒的性质及应用", 《SCIENCE & TECHNOLOGY INFORMATION》 * |
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Application publication date: 20200117 |