CN110713735A - Preparation method of high-temperature-resistant and solvent-resistant yellow fluorescent pigment - Google Patents
Preparation method of high-temperature-resistant and solvent-resistant yellow fluorescent pigment Download PDFInfo
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- CN110713735A CN110713735A CN201910978473.1A CN201910978473A CN110713735A CN 110713735 A CN110713735 A CN 110713735A CN 201910978473 A CN201910978473 A CN 201910978473A CN 110713735 A CN110713735 A CN 110713735A
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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
- C09B67/006—Preparation of organic pigments
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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
- C09B67/0001—Post-treatment of organic pigments or dyes
- C09B67/0003—Drying, e.g. sprax drying; Sublimation of the solvent
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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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
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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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
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Abstract
The invention relates to a fluorescent pigment, in particular to a high-temperature resistant and solvent-resistant organic or inorganic lemon yellow fluorescent pigment. Step 1: the method comprises the steps of hydrothermally synthesizing a series of layered silicate matrixes with definite parameters, analyzing and determining chemical composition, granularity, cation exchange capacity, expansion capacity, interlamellar spacing, interlayer ion type and quantity, basic physical and chemical performance parameters of layer charge and structural data, and providing basic materials and basic data for subsequent preparation and target product research; step 2: the synthesized phyllosilicate matrix is reacted with organic reactants screened by experiments to prepare a material with grafted end faces; and step 3: carrying out ion exchange, adsorption or solvation on a carbon-nitrogen polymer precursor, introducing the carbon-nitrogen polymer precursor into a layered silicate matrix, and carrying out high-temperature roasting to gradually carry out polycondensation between layers to generate the g-C3N 4/layered silicate composite material; and 4, step 4: and (3) soaking the synthesized g-C3N 4/layered silicate composite material in a fluorescent yellow dye solution to prepare the fluorescent yellow pigment.
Description
Technical Field
The invention relates to a fluorescent pigment, in particular to a high-temperature resistant and solvent-resistant organic or inorganic lemon yellow fluorescent pigment.
Background
Organic fluorescent pigments, also known as daylight fluorescent pigments, are an emerging branch of organic pigments in the field of the fastest development in the world and at home in recent years. After absorbing visible light and ultraviolet light, the organic fluorescent pigment can convert the ultraviolet light which cannot be felt by human eyes into visible light with a certain color through the internal electronic energy level conversion, the light is superposed with the reflected light of the pigment, the emitted light has much higher brightness than that of the common pigment, and the intensity can reach three times of that of the common pigment, so that the very bright color is formed. This color is very attractive in many application scenarios. Therefore, fluorescent pigments are widely used in the industries of coatings, paints, inks, plastics coloring, and the like. In the last two decades, with the development of the world economy, the quality of life of people is continuously improved, and the demand of fluorescent pigments is very vigorous at home and abroad. According to incomplete statistics, the production and sales of organic fluorescent pigments are rapidly increasing at a rate of 30-40% per year. In recent years, the demand for fluorescent pigments for high-grade sports products, high-grade children's toys, stationery, advertising, decorative ornaments, safety identification articles and military products has increased explosively. Related products containing fluorescent pigment elements are developed into a series of high-end products in the industry, and also are a product series with high profit margin, and an economic growth system taking fluorescent pigment as a core is formed. In 2018, the worldwide fluorescent pigment sales exceeds 15 million tons, and at present, manufacturers of Asian fluorescent pigments mainly concentrate on China, India and Japan, and with the explosive growth of China's demand for fluorescent pigments, the market prospects of the fluorescent pigments will become very wide.
The organic fluorescent pigment consists of fluorescent dye, carrier resin, assistant, etc. Fluorescent dyes are the main cause of pigment color development, and the stability of fluorescent dyes is poor. The carrier is a fluorescent dye fixing agent, usually in order to improve the stability of the fluorescent dye. The traditional carrier for fluorescent pigments is a p-toluenesulfonamide-formaldehyde-melamine system. It has the advantages of easy pulverization, good compatibility with dye, bright color, strong tinting strength, etc., but also has poor heat resistance and is extremely unstable at more than 180 ℃; poor light fastness (around grade 2); is not friendly to the environment, and has formaldehyde release in the production and use processes; has the defects of large bleeding phenomenon and the like after molding. In order to improve the above disadvantages, carriers such as polyester resins, polyester amide resins, polyamide resins, acrylic resins, etc. have been developed in the 70 th 20 th century, and these resins have various disadvantages such as poor heat resistance and solvent resistance.
At present, most of fluorescent pigments in China mainly use a p-toluenesulfonamide-formaldehyde-melamine system as a carrier, and although products synthesized by the method have the advantages of easiness in crushing, good dye compatibility, strong tinting strength, bright color and the like, the problems of poor temperature resistance, poor solvent resistance and the like exist in the production and use processes, and the use range of the formaldehyde-containing fluorescent pigments is limited. The solvent resistance and heat resistance of fluorescent pigments using polyester, polyamide, etc. as carriers are still to be improved when the fluorescent pigments are used. Under the background, the development of fluorescent pigments without formaldehyde, with high temperature resistance and strong solvent resistance will become the main development direction of the fluorescent pigment industry in the future.
Disclosure of Invention
In order to overcome the defects of the background art, the invention aims to provide a preparation method of a yellow fluorescent pigment with high temperature resistance and strong solvent resistance.
The technical scheme adopted by the invention is as follows: a preparation method of a high-temperature-resistant and solvent-resistant fluorescent yellow pigment is characterized by comprising the following steps: the method comprises the following steps:
step 1: the method comprises the steps of hydrothermally synthesizing a series of layered silicate matrixes with definite parameters, analyzing and determining chemical composition, granularity, cation exchange capacity, expansion capacity, interlamellar spacing, interlayer ion type and quantity, basic physical and chemical performance parameters of layer charge and structural data, and providing basic materials and basic data for subsequent preparation and target product research;
step 2: carrying out experimental screening on the phyllosilicate substrate synthesized in the step 1, and reacting organic reactants to prepare a material with grafted end faces;
and step 3: introducing the precursor of the carbon-nitrogen polymer into the layered silicate matrix in the step 2 through ion exchange, adsorption or solvation, and gradually polycondensing the precursor of the carbon-nitrogen polymer at high temperature to generate the g-C3N 4/layered silicate composite material;
and 4, step 4: soaking the synthesized g-C3N 4/layered silicate composite material in a fluorescent yellow dye solution to prepare a fluorescent yellow pigment;
and 5: removing most of medium water and solvent of the fluorescent yellow pigment obtained in the step 4 through filter pressing;
step 6: further removing other impurities of the fluorescent yellow pigment in the step 5 by washing;
and 7: the water content of the fluorescent yellow pigment product is less than 2 percent through dynamic vacuum drying dehydration;
and 8: and separating a small amount of pigment aggregates by using gas powder to finally obtain the finished fluorescent yellow pigment with uniform particles.
Preferably, the organic reactant in the step 2 is an organosilicon reagent with a structure of-R-Si-O-, and the grafting product is generated by the end grafting reaction by utilizing the hydrolytic condensation of the broken bonds of R-Si-O-and the end Si-O of the layered silicate.
Preferably, the carbon-nitrogen polymer precursor in step 3 is one or more of melamine (C3N3(NH2)3), dicyandiamide (H4C2N4), ammonium azide (NH4[ N (CN)2]), or cyanamide (H2CN 2).
Preferably, the phyllosilicate is one or more of montmorillonite, saponite, sepiolite or illite.
The invention has the beneficial effects that: 1. the project takes a carbon nitrogen material (g-C3N 4) as a fluorescence enhancement additive, and g-C3N4 is a non-metal hybrid material with metal characteristics and has excellent solvent resistance and temperature resistance. Moreover, electrons delocalized on the surface of the fluorescent yellow dye can form a large pi bond, so that the fluorescent yellow dye which also has a conjugated system is very favorable for affinity with the fluorescent yellow dye, and the chromatic light effect of the product is improved by reducing the fluorescence quenching effect.
2. The invention takes the phyllosilicate material as a carrier, has large specific surface area (500-. Therefore, the fluorescent dye is placed between layers of the phyllosilicate, so that dye molecules can be highly dispersed between the layers, the dispersion degree is improved, the fluorescent dye can be protected, the temperature resistance is improved, and the fluorescence intensity can be improved.
3. Fluorescent pigments exhibit a brilliant color due to their ability to absorb ultraviolet light. However, it is this property that makes it sensitive to intense light and high temperature aerobic environments. If the abovementioned disadvantages are avoided as far as possible in the production stage, fluorescent pigment products having excellent shade can be produced. The final product of the project is a powder substance, and the intermediate product must be heated and dried in the production process.
Detailed Description
The invention provides a preparation method of a high-temperature-resistant and solvent-resistant fluorescent yellow pigment, which comprises the following steps:
step 1: the method comprises the steps of hydrothermally synthesizing a series of layered silicate matrixes with definite parameters, analyzing and determining chemical composition, granularity, cation exchange capacity, expansion capacity, interlamellar spacing, interlayer ion type and quantity, basic physical and chemical performance parameters of layer charge and structural data, and providing basic materials and basic data for subsequent preparation and target product research;
step 2: carrying out experimental screening on the phyllosilicate substrate synthesized in the step 1, and reacting organic reactants to prepare a material with grafted end faces;
and step 3: introducing the precursor of the carbon-nitrogen polymer into the layered silicate matrix in the step 2 through ion exchange, adsorption or solvation, and gradually polycondensing the precursor of the carbon-nitrogen polymer at high temperature to generate the g-C3N 4/layered silicate composite material;
and 4, step 4: soaking the synthesized g-C3N 4/layered silicate composite material in a fluorescent yellow dye solution to prepare a fluorescent yellow pigment;
and 5: removing most of medium water and solvent of the fluorescent yellow pigment obtained in the step 4 through filter pressing;
step 6: further removing other impurities of the fluorescent yellow pigment in the step 5 by washing;
and 7: the water content of the fluorescent yellow pigment product is less than 2 percent through dynamic vacuum drying dehydration;
and 8: and separating a small amount of pigment aggregates by using gas powder to finally obtain the finished fluorescent yellow pigment with uniform particles.
The organic reactant in the step 2 is an organic silicon reagent with a-R-Si-O-structure, and the hydrolysis condensation of the broken bonds of the R-Si-O-and the layered silicate end face Si-O is utilized to carry out the end face grafting reaction to generate a grafting product.
The precursor of the carbon-nitrogen polymer in the step 3 is one or more of melamine (C3N3(NH2)3), dicyandiamide (H4C2N4), ammonium azide (NH4[ N (CN)2]), and cyanamide (H2CN 2).
The phyllosilicate is one or more of montmorillonite, saponite, sepiolite or illite.
The dye is a colorant of a fluorescent pigment. The selection of the dye directly influences the color of the finished product, and the selection standard of the dye requires good transparency, bright color and good compatibility with resin. The dye selected by the invention is solvent yellow dye. The dye belongs to a solvent type fluorescent dye, has high heat resistance, is insoluble in water and soluble in an organic solvent, and has the following advantages: the lemon yellow fluorescent pigment molecule conjugated system has good interaction with the conjugated system of the g-C3N4 nano-sheet, so that the fluorescent efficiency of the product is high, and the color is more gorgeous. The dye is the prior art, and specifically refers to an invention patent applied by my company on 3/29/2013, with the patent name: the solvent yellow dye for the environment-friendly fluorescent pigment has the following patent numbers: 201310105888.0.
Silicate matrixes with different microscopic grain diameters and different charge properties are obtained through control of a hydrothermal synthesis process and the like, target product samples with end grafting and interlayer insertion are prepared through experiments, the composition is analyzed, and the structural morphology of the product is represented. The influence and the effect of the microscopic particle size of a matrix, layer charge and end surface charge on end surface grafting and interlayer intercalation are mainly analyzed, and the regularity of the control change of the matrix on products is known. The influence of the types, concentrations, preparation flows and the like of carbon and nitrogen raw materials on the structure of the grain size, C/N ratio and the like of the synthesized g-C3N4 is examined. The influence rule of the phyllosilicate/g-C3N 4/fluorescent dye ratio on the fluorescence intensity is analyzed. Through formula design and small tests, the optimal layered silicate carrier and the optimal molar ratio of the three monomers are determined, the advantages of the three monomers are exerted to the maximum extent, and the synthesized fluorescent pigment has high performance and quality.
The project takes a carbon nitrogen material (g-C3N 4) as a fluorescence enhancement additive, and g-C3N4 is a non-metal hybrid material with metal characteristics and has excellent solvent resistance and temperature resistance. Moreover, electrons delocalized on the surface of the fluorescent yellow dye can form a large pi bond, so that the fluorescent yellow dye which also has a conjugated system is very favorable for affinity with the fluorescent yellow dye, and the chromatic light effect of the product is improved by reducing the fluorescence quenching effect.
The invention takes the phyllosilicate material as a carrier, has large specific surface area (500-. Therefore, the fluorescent dye is placed between layers of the phyllosilicate, so that dye molecules can be highly dispersed between the layers, the dispersion degree is improved, the fluorescent dye can be protected, the temperature resistance is improved, and the fluorescence intensity can be improved.
Fluorescent pigments exhibit a brilliant color due to their ability to absorb ultraviolet light. However, it is this property that makes it sensitive to intense light and high temperature aerobic environments. If the abovementioned disadvantages are avoided as far as possible in the production stage, fluorescent pigment products having excellent shade can be produced. The final product of the project is a powder substance, and the intermediate product must be heated and dried in the production process.
The main technical indexes of the invention are as follows:
1. shade (vs standard): is superior to the standard sample;
2. tinting strength (compared to standard): 100 plus or minus 5 percent;
3. fineness (D50): less than or equal to 3 mu m;
4. temperature resistance: foaming and sampling EVA at 190 deg.C for 5 min.
5. Solvent resistance: butanone soaking: and IV stage.
The skilled person should understand that: although the invention has been described in terms of the above specific embodiments, the inventive concept is not limited thereto and any modification applying the inventive concept is intended to be included within the scope of the patent claims.
Claims (4)
1. A preparation method of a high-temperature-resistant and solvent-resistant fluorescent yellow pigment is characterized by comprising the following steps: the method comprises the following steps:
step 1: the method comprises the steps of hydrothermally synthesizing a series of layered silicate matrixes with definite parameters, analyzing and determining chemical composition, granularity, cation exchange capacity, expansion capacity, interlamellar spacing, interlayer ion type and quantity, basic physical and chemical performance parameters of layer charge and structural data, and providing basic materials and basic data for subsequent preparation and target product research;
step 2: carrying out experimental screening on the phyllosilicate substrate synthesized in the step 1, and reacting organic reactants to prepare a material with grafted end faces;
and step 3: introducing the precursor of the carbon-nitrogen polymer into the layered silicate matrix in the step 2 through ion exchange, adsorption or solvation, and gradually polycondensing the precursor of the carbon-nitrogen polymer at high temperature to generate the g-C3N 4/layered silicate composite material;
and 4, step 4: soaking the synthesized g-C3N 4/layered silicate composite material in a fluorescent yellow dye solution to prepare a fluorescent yellow pigment;
and 5: removing most of medium water and solvent of the fluorescent yellow pigment obtained in the step 4 through filter pressing;
step 6: further removing other impurities of the fluorescent yellow pigment in the step 5 by washing;
and 7: the water content of the fluorescent yellow pigment product is less than 2 percent through dynamic vacuum drying dehydration;
and 8: and separating a small amount of pigment aggregates by using gas powder to finally obtain the finished fluorescent yellow pigment with uniform particles.
2. The method for preparing the high temperature and solvent resistant fluorescent yellow pigment according to claim 1, wherein the method comprises the following steps: the organic reactant in the step 2 is an organic silicon reagent with a-R-Si-O-structure, and the hydrolysis condensation of the broken bonds of the R-Si-O-and the layered silicate end face Si-O is utilized to carry out the end face grafting reaction to generate a grafting product.
3. The method for preparing a high temperature and solvent resistant fluorescent yellow pigment according to claim 1 or 2, wherein the method comprises the following steps: the precursor of the carbon-nitrogen polymer in the step 3 is one or more of melamine (C3N3(NH2)3), dicyandiamide (H4C2N4), ammonium azide (NH4[ N (CN)2]), and cyanamide (H2CN 2).
4. The method for preparing a high temperature and solvent resistant fluorescent yellow pigment according to claim 1 or 2, wherein the method comprises the following steps: the phyllosilicate is one or more of montmorillonite, saponite, sepiolite or illite.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113583479A (en) * | 2021-06-29 | 2021-11-02 | 福建师范大学 | Method for preparing silver pearlescent pigment by using solid waste generated in process of processing inkstone pot |
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2019
- 2019-10-15 CN CN201910978473.1A patent/CN110713735A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113583479A (en) * | 2021-06-29 | 2021-11-02 | 福建师范大学 | Method for preparing silver pearlescent pigment by using solid waste generated in process of processing inkstone pot |
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