CN111848917A - Preparation method and application of polyurea fluorescent microsphere pigment - Google Patents
Preparation method and application of polyurea fluorescent microsphere pigment Download PDFInfo
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- CN111848917A CN111848917A CN202010806061.2A CN202010806061A CN111848917A CN 111848917 A CN111848917 A CN 111848917A CN 202010806061 A CN202010806061 A CN 202010806061A CN 111848917 A CN111848917 A CN 111848917A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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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
- C09B69/00—Dyes not provided for by a single group of this subclass
- C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular 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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
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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
- C09K2211/14—Macromolecular compounds
- C09K2211/1408—Carbocyclic compounds
- C09K2211/1416—Condensed systems
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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
- C09K2211/14—Macromolecular compounds
- C09K2211/1441—Heterocyclic
- C09K2211/145—Heterocyclic containing oxygen as the only heteroatom
Abstract
The invention belongs to the technical field of pigment preparation, particularly relates to a preparation method of a polymer fluorescent microsphere pigment, and more particularly relates to a polyurea microsphere pigment with a daylight fluorescent effect prepared by a suspension polymerization method. The preparation method comprises the following steps: (1) adding the composite emulsifier into water, heating and stirring until the emulsifier is completely dissolved; adding the fluorescent dye, continuing stirring until the dye is dissolved, and cooling for later use; (2) pouring isophorone diisocyanate into water, adding the material obtained in the step (1), and reacting to form a linear polyurea microsphere pigment suspension; (3) separating the slag water of the suspension obtained in the step (2) to obtain a pigment filter cake containing water, and washing the filter cake with water; (4) and (4) drying the filter cake washed in the step (3). The microsphere pigment obtained by the invention has excellent high temperature resistance and better solvent resistance; the pigment has better migration resistance and is environment-friendly.
Description
Technical Field
The invention belongs to the technical field of pigment preparation, particularly relates to a preparation method of a polymer fluorescent microsphere pigment, and more particularly relates to a polyurea microsphere pigment with a daylight fluorescent effect prepared by a suspension polymerization method, and also relates to an application of the pigment.
Background
A daylight fluorescent pigment (hereinafter referred to as fluorescent pigment) is a special organic pigment which can emit bright colors under the irradiation of sunlight or shorter wavelength light and is widely used for coloring plastics, paint ink, candles and textiles. The fluorescent pigment is composed of carrier resin and fluorescent dye, wherein the fluorescent dye gives fluorescent effect to the pigment, and the carrier resin determines the solvent resistance, migration resistance, temperature resistance and the like of the pigment. The common fluorescent pigments in the market at present are classified into polyester type, polyamide type, melamine formaldehyde resin type, styrene-acrylic emulsion, and the like according to the carrier resin. Polyester, polyamide and styrene-acrylic emulsion can only be used in the plastic coloring field due to poor solvent resistance of resin and low softening point (< 150 ℃) of the resin. Although the melamine formaldehyde resin type fluorescent pigment has high internal crosslinking degree, crosslinked ether bonds still cannot resist the damage of ketone and other strong solvents, and the melamine resin has low decomposition point (< 250 ℃), is easy to release formaldehyde and limits the use of the melamine resin type fluorescent pigment. In addition, most of the conventional fluorescent pigment synthesis methods are formed by blending a carrier resin and a fluorescent dye, but the dye is difficult to prevent from precipitating from the resin by the simple physical coating, so the migration resistance is also poor.
According to the reports of Jinjin Xu et al (RSC Advance, 2014, 4(61), 32134-32141), the polyurea resin microspheres have very excellent heat resistance, and thermogravimetric analysis shows that the linear polyurea resin microspheres can be kept stable at a temperature below 280 ℃, and only lose 5% weight at a high temperature of 330 ℃. In addition, the polyurea resin has more active groups and good affinity to dyes, and is often used in sewage treatment processes such as dye adsorption and the like.
Patent document CN107286314 reports a porous cross-linked polyurea microsphere and a preparation method thereof. The author takes silicon dioxide as a template, takes isophorone diisocyanate and triethylene tetramine as raw materials, and prepares the polyurea microspheres in a mixed solvent of water and acetone. The microspheres have porosity and can be used for treating dye sewage. Patent document CN 104356344 discloses a food rich inA preparation method of amino monodisperse porous microspheres. The author takes silica particles as a template, uses isophorone diisocyanate as a single raw material, and prepares the polyurea microspheres in a mixed solvent of water and acetone by a precipitation polymerization method. The porous polyurea microspheres obtained by etching the silicon dioxide in the polyurea microspheres with alkali can be used in the fields of enzyme immobilization, chemical catalysis, dye and heavy metal separation and adsorption and the like. The preparation of polyurea fluorescent microspheres has also been studied. Gongming Hui et al (the report of chemical schools higher, 2019, 40(6), 1317-1323) reported that highly monodisperse fluorescent polyurea microspheres with clean surfaces are prepared by precipitation polymerization in a water/acetone mixed solvent by using isophorone diisocyanate as a monomer and amino-functionalized 1, 8-naphthalimide as a fluorescent group. Fe at different concentrations according to polyurea fluorescent microspheres3+The difference of fluorescence intensity in solution can be used for Fe3+Detection of (3).
In the above-mentioned journal literature and patent literature, although they solve the technical problem in one aspect, the following unsolved technical problems still exist:
1. the high temperature resistance is not strong: the existing melamine formaldehyde resin fluorescent pigment has low decomposition point and is not suitable for being applied to the field of high-temperature leak detection;
2. poor solvent resistance: the existing melamine formaldehyde resin fluorescent pigment has poor solvent resistance, can only resist weak solvents such as alcohols, esters and the like, and has a narrow application range;
3. poor migration resistance: the prior preparation method of the fluorescent pigment mostly adopts a method of physically blending resin and fluorescent dye, and the chemical bonding of the dye and the resin is less, so that the dye cannot be fixed on carrier resin, and the dye is migrated;
4. the environmental protection property is poor: the melamine formaldehyde resin fluorescent pigment contains formaldehyde, and is easy to cause great pollution to the environment.
Therefore, in order to solve the technical problems which are not solved by the above solutions, it is necessary to invent an environment-friendly pigment with excellent high temperature resistance, solvent resistance and migration resistance.
Disclosure of Invention
In order to solve the technical problems, the invention provides a polyurea microsphere pigment with a daylight fluorescent effect.
The invention provides a preparation method of a polyurea fluorescent microsphere pigment, which comprises the following steps:
(1) adding the composite emulsifier into water, heating and stirring until the emulsifier is completely dissolved; adding the fluorescent dye, continuing stirring until the dye is dissolved, and cooling for later use;
(2) pouring isophorone diisocyanate into water, adding the material obtained in the step (1), and reacting to form a linear polyurea microsphere pigment suspension;
(3) separating the slag water of the suspension obtained in the step (2) to obtain a pigment filter cake containing water, and washing the filter cake with water;
(4) and (4) drying the filter cake washed in the step (3).
Preferably, in the step (1), the temperature is increased to 65-75 ℃ and the mixture is stirred for 0.8-1.2 h; the composite emulsifier is a nonionic emulsifier and an anionic emulsifier, and the weight part ratio of the nonionic emulsifier to the anionic emulsifier is 1: 2-3, the ratio of the composite emulsifier to the water is 0.5-1.2: 100.
(1) the fluorescent dye is selected from fluorescent dyes with amino or hydroxyl. More preferably, the fluorescent dye comprises basic red 1, basic red 1: 1. at least one of solvent violet 9 and solvent yellow 172; the fluorescent dye accounts for 0-15% of the mass of the isophorone diisocyanate.
(1) Adding the dye, continuously stirring for 8-12 min until the dye is completely dissolved, and then cooling to 38-45 ℃ for later use.
(2) The weight ratio of the isophorone diisocyanate to the composite emulsifier is 9-12: 1; the reaction time is 19-21 hours, and the emulsifying machine is started to operate at the rotating speed of 5000r/min during the reaction.
(3) And (3) carrying out slag-water separation on the suspension obtained in the step (2) by adopting a centrifugal machine or a suction filtration mode to obtain a water-containing pigment filter cake, and washing the filter cake with water.
(4) And drying at 100-110 ℃.
The preparation method of the polyurea fluorescent microsphere pigment comprises the following steps:
(1) adding the composite emulsifier into water, heating to 65-75 ℃, and stirring for 0.8-1.2 h until the emulsifier is completely dissolved; adding the fluorescent dye, continuing stirring until the dye is dissolved, and cooling for later use;
the composite emulsifier is a nonionic emulsifier and an anionic emulsifier, and the weight part ratio of the nonionic emulsifier to the anionic emulsifier is 1: 2-3, the ratio of the composite emulsifier to the water is 0.5-1.2: 100, respectively; the fluorescent dye is selected from fluorescent dyes with amino or hydroxyl;
(2) pouring isophorone diisocyanate into water, adding the material obtained in the step (1), and reacting to form a linear polyurea microsphere pigment suspension; wherein the weight ratio of the isophorone diisocyanate to the composite emulsifier is 9-12: 1; the reaction time is 19-21 hours, and the emulsifying machine is started to operate at the rotating speed of 5000r/min during the reaction;
(3) performing slag-water separation on the suspension obtained in the step (2) by adopting a centrifugal machine or a suction filtration mode to obtain a water-containing pigment filter cake, and washing the filter cake twice by using water;
(4) drying the washed filter cake in the step (3) at the temperature of 100-110 ℃.
Preferably, the preparation method of the polyurea fluorescent microsphere pigment comprises the following steps:
(1) adding the composite emulsifier into water, heating to 70 ℃, and stirring for 1h until the emulsifier is completely dissolved; adding the fluorescent dye, continuing stirring until the dye is dissolved, and cooling for later use;
the composite emulsifier is a nonionic emulsifier and an anionic emulsifier, and the weight part ratio of the nonionic emulsifier to the anionic emulsifier is 3: 7, the proportion of the composite emulsifier to the water is 1: 125; the fluorescent dye is selected from basic red 1: 1;
(2) pouring isophorone diisocyanate into water, adding the material obtained in the step (1), and reacting to form a linear polyurea microsphere pigment suspension; wherein the weight ratio of the isophorone diisocyanate to the composite emulsifier is 11.1: 1; the reaction time is 20 hours, and the emulsifying machine is started to operate at the rotating speed of 5000r/min during the reaction;
(3) performing slag-water separation on the suspension obtained in the step (2) by adopting a centrifugal machine or a suction filtration mode to obtain a water-containing pigment filter cake, and washing the filter cake twice by using water;
(4) and (4) drying the washed filter cake in the step (3) at 105 ℃.
The application of the polyurea fluorescent microsphere pigment prepared by the method in high-temperature fluorescent leak detection, paint ink, color paste and plastic is also the technical problem to be solved by the invention.
The invention has the beneficial effects that:
the microsphere pigment has higher decomposition point (more than 280 ℃) and excellent high-temperature resistance, so that the microsphere pigment can be applied to the field of high-temperature leak detection; and better solvent resistance (strong solvents such as alcohols, ethers, esters, acetone, butanone and the like), avoids the swelling of the pigment in the paint ink, and also has wider solvent selection range of the fluorescent paint ink.
In addition, the raw material isophorone diisocyanate reacts with the fluorescent dye with hydroxyl or amino after screening, so that the dye molecule is connected to the polyurea main chain. Compared with the traditional physical mixing and coating, the migration resistance of the pigment is better; and because the pigment does not contain pollutants such as formaldehyde, the pigment is environment-friendly.
Detailed Description
The present invention will now be further described with reference to specific embodiments in order to enable those skilled in the art to better understand the present invention.
Example 1
The preparation method of the polyurea fluorescent microsphere pigment comprises the following steps:
adding the composite emulsifier (1.2 g of nonionic emulsifier and 2.8g of anionic emulsifier) into 500g of water, heating to 70 ℃, and stirring for 1h to ensure that the emulsifier is completely dissolved. Adding basic red 1: 1(0.5g) and stirring is continued for 10min to completely dissolve the dye. Then cooling to 40 ℃ for later use.
44.4g of the weighed isophorone diisocyanate was poured into water, and the emulsifying machine was turned on at 5000 r/min. After the reaction is continued for 20h, relatively uniform polyurea microspheres can be observed. D10 ═ 22.7 μm, D50 ═ 41.4 μm, and D90 ═ 57.5 μm. And (3) separating the suspension by using a centrifugal machine or suction filtration to obtain a water-containing pigment filter cake, washing twice by using water, and drying at 105 ℃ to obtain the polyurea fluorescent microsphere pigment.
Observing and detecting the product, and finding that the obtained product has narrow microsphere distribution and uniform shape.
Comparative example 1
The fluorescent dye basic red 1: 1. stirring is continued for 10min to completely dissolve the dye. 44.4g of weighed isophorone diisocyanate is poured into water, the emulsifying machine is started at the same time for 5000r/min, the reaction is continued for 20h, and sampling observation shows that the materials are irregular in shape with different sizes and have no microspheres.
As can be seen from comparative example 1, no microspherical product could be obtained without the use of an emulsifier, indicating that the emulsifier plays a significant role in the formation of the microspheres.
Comparative example 2
Adding composite emulsifier (0.6 g nonionic emulsifier and 1.4g anionic emulsifier) into 500g water, heating to 70 deg.C, and stirring for 1h to ensure complete dissolution of the emulsifier. Adding basic red 1: 1, stirring for 10min to completely dissolve the dye. Then cooling to 40 ℃ for later use. 44.4g of the weighed isophorone diisocyanate was poured into water, and the emulsifying machine was turned on at 5000 r/min. The reaction is continued for 20h, polyurea microspheres can be observed, but the particle size distribution of the microspheres is wide. The particle size distribution of the tested sample D10-34.2 μm, D50-84 μm and D90-175 μm. And separating the suspension by using a centrifuge or suction filtration to obtain a pigment filter cake containing water, washing twice by using water, and drying at 105 ℃.
In comparative example 2, the amount of the emulsifier used was less than that in example 1, and the obtained microspheres had a coarse particle size and a wide distribution. It can be seen that the proper amount of emulsifier plays a large role in product morphology and distribution.
Comparative example 3
Adding the composite emulsifier (1.2 g of nonionic emulsifier and 2.8g of anionic emulsifier) into 500g of water, heating to 70 ℃, and stirring for 1h to ensure that the emulsifier is completely dissolved. Adding basic red 1: 1. in that respect Stirring is continued for 10min to completely dissolve the dye. Without cooling, 44.4g of the weighed isophorone diisocyanate is poured into water, and the emulsifying machine is opened at 5000 r/min. After 4h of reaction the material was found to agglomerate severely and the solution was very viscous.
In comparative example 3, after the dye was dissolved, no temperature reduction treatment was performed, and the result shows that the material was very severely agglomerated; compared with the embodiment 1, the scheme has the advantages that the temperature reduction treatment is timely carried out after the dye is dissolved, the product is uniform, and no agglomeration exists. This indicates that the effect of temperature on the pigment product is also significant.
Comparative example 4
Adding the composite emulsifier (1.4 g of nonionic emulsifier and 2.8g of anionic emulsifier) into 500g of water, heating to 70 ℃, and stirring for 1h to ensure that the emulsifier is completely dissolved. Adding basic red 1: 1. 6.18g of amino curing agent diethylenetriamine is continuously added, and the stirring is continued for 10 min. The temperature is reduced to 40 ℃, 44.4g of the weighed isophorone diisocyanate is poured into water, and meanwhile, the emulsifying machine is started for 5000 r/min. The reaction time was 12h and the particles were observed to be finer and irregularly shaped. D10 ═ 3.2 μm, D50 ═ 8.4 μm, and D90 ═ 12.9 μm. And separating the suspension by using a centrifuge or suction filtration to obtain a pigment filter cake containing water, washing twice by using water, and drying at 105 ℃.
In comparative example 4, the use of an amino curing agent can shorten the reaction time, but microspheres are not obtained.
Example 2
1. And (3) solvent resistance test: 1g of the powder is added to 15g of the solvent and shaken up. The state of the pigment in the solvent was observed for 24 h.
2. And (3) testing the mobility: 0.36g of pigment was added to 150g of PVC resin pellets to prepare injection-molded plaques at 170 ℃ and the plaques were pressed together with a blank plaque (without pigment) in an oven at 60 ℃ for 48 hours. The shade of the dyeing on the blank injection molded plate was compared and the migration of the pigment was judged by the shade of the color. The darker the color, the poorer the pigment migration.
The pigment is applied to the field of high-temperature leak detection, and the following requirements are required to be met: firstly, the pigment cannot be softened, i.e. cannot have a softening point; at the same time, the decomposition point of the pigment is high.
Compared with the prior art, the polyurea microsphere pigment with the daylight fluorescent effect is prepared by a suspension polymerization method. The microsphere pigment has higher decomposition point (more than 280 ℃) and better solvent resistance (strong solvents such as alcohols, ethers, esters, acetone, butanone and the like). The raw material isophorone diisocyanate reacts with the fluorescent dye with hydroxyl or amino after screening, so that dye molecules are connected to a polyurea main chain. The pigments have better migration resistance than conventional physical mixing and coating.
Compared with the comparative example, whether the emulsifier is adopted, the dosage, the temperature and the like can have obvious influence on the pigment product, and the obtained pigment is an ideal product only under the raw material proportion and the process parameters of the invention.
Claims (10)
1. A preparation method of a polyurea fluorescent microsphere pigment comprises the following steps:
(1) adding the composite emulsifier into water, heating and stirring until the emulsifier is completely dissolved; adding the fluorescent dye, continuing stirring until the dye is dissolved, and cooling for later use;
(2) pouring isophorone diisocyanate into water, adding the material obtained in the step (1), and reacting to form a linear polyurea microsphere pigment suspension;
(3) separating the slag water of the suspension obtained in the step (2) to obtain a pigment filter cake containing water, and washing the filter cake with water;
(4) and (4) drying the filter cake washed in the step (3).
2. The method for preparing the polyurea fluorescent microsphere pigment according to claim 1, wherein in the step (1), the temperature is increased to 65-75 ℃ and the mixture is stirred for 0.8-1.2 h; the composite emulsifier is a nonionic emulsifier and an anionic emulsifier, and the weight part ratio of the nonionic emulsifier to the anionic emulsifier is 1: 2-3, the ratio of the composite emulsifier to the water is 0.5-1.2: 100.
3. the method for preparing a polyurea fluorescent microsphere pigment according to claim 1, wherein in (1), the fluorescent dye is selected from fluorescent dyes with amino or hydroxyl, preferably, the fluorescent dye comprises basic red 1, basic red 1: 1. at least one of solvent violet 9 and solvent yellow 172;
the fluorescent dye accounts for 0-15% of the mass of isophorone diisocyanate.
4. The method for preparing the polyurea fluorescent microsphere pigment according to claim 1, wherein in the step (1), the dye is added, then the stirring is continued for 8-12 min until the dye is completely dissolved, and then the temperature is reduced to 38-45 ℃ for standby.
5. The method for preparing the polyurea fluorescent microsphere pigment according to claim 1, wherein the weight ratio of the isophorone diisocyanate to the composite emulsifier in (2) is 9-12: 1; the reaction time is 19-21 hours, and the emulsifying machine is started to operate at the rotating speed of 5000r/min during the reaction.
6. The method for preparing the polyurea fluorescent microsphere pigment according to claim 1, wherein (3) the suspension obtained in (2) is subjected to slag-water separation by a centrifuge or suction filtration to obtain an aqueous pigment filter cake, and the filter cake is washed by water.
7. The method for preparing the polyurea fluorescent microsphere pigment according to claim 1, wherein in the step (4), the polyurea fluorescent microsphere pigment is dried at 100-110 ℃.
8. The method for preparing the polyurea fluorescent microsphere pigment according to claim 1, comprising the following steps:
(1) adding the composite emulsifier into water, heating to 65-75 ℃, and stirring for 0.8-1.2 h until the emulsifier is completely dissolved; adding the fluorescent dye, continuing stirring until the dye is dissolved, and cooling for later use;
the composite emulsifier is a nonionic emulsifier and an anionic emulsifier, and the weight part ratio of the nonionic emulsifier to the anionic emulsifier is 1: 2-3, the ratio of the composite emulsifier to the water is 0.5-1.2: 100, respectively; the fluorescent dye is selected from fluorescent dyes with amino or hydroxyl;
(2) pouring isophorone diisocyanate into water, adding the material obtained in the step (1), and reacting to form a linear polyurea microsphere pigment suspension; wherein the weight ratio of the isophorone diisocyanate to the composite emulsifier is 9-12: 1; the reaction time is 19-21 hours, and the emulsifying machine is started to operate at the rotating speed of 5000r/min during the reaction;
(3) performing slag-water separation on the suspension obtained in the step (2) by adopting a centrifugal machine or a suction filtration mode to obtain a water-containing pigment filter cake, and washing the filter cake twice by using water;
(4) drying the washed filter cake in the step (3) at the temperature of 100-110 ℃.
9. The method for preparing the polyurea fluorescent microsphere pigment according to claim 1, comprising the following steps:
(1) adding the composite emulsifier into water, heating to 70 ℃, and stirring for 1h until the emulsifier is completely dissolved; adding the fluorescent dye, continuing stirring until the dye is dissolved, and cooling for later use;
the composite emulsifier is a nonionic emulsifier and an anionic emulsifier, and the weight part ratio of the nonionic emulsifier to the anionic emulsifier is 3: 7, the proportion of the composite emulsifier to the water is 1: 125; the fluorescent dye is selected from basic red 1: 1;
(2) pouring isophorone diisocyanate into water, adding the material obtained in the step (1), and reacting to form a linear polyurea microsphere pigment suspension; wherein the weight ratio of the isophorone diisocyanate to the composite emulsifier is 11.1: 1; the reaction time is 20 hours, and the emulsifying machine is started to operate at the rotating speed of 5000r/min during the reaction;
(3) performing slag-water separation on the suspension obtained in the step (2) by adopting a centrifugal machine or a suction filtration mode to obtain a water-containing pigment filter cake, and washing the filter cake twice by using water;
(4) and (4) drying the washed filter cake in the step (3) at 105 ℃.
10. The polyurea fluorescent microsphere pigment prepared by the method of claim 1 is applied to high-temperature fluorescent leak detection, paint ink, color paste and plastic cement.
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Denomination of invention: Preparation method and application of a polyurea fluorescent microsphere pigment Effective date of registration: 20230627 Granted publication date: 20220401 Pledgee: China Postal Savings Bank Limited by Share Ltd. Shexian branch Pledgor: HUANGSHAN JIAJIA FLUORESCENT MATERIAL CO.,LTD. Registration number: Y2023980046063 |