CN112250779A - Photochromic microspheres, preparation method and application - Google Patents
Photochromic microspheres, preparation method and application Download PDFInfo
- Publication number
- CN112250779A CN112250779A CN202011165744.0A CN202011165744A CN112250779A CN 112250779 A CN112250779 A CN 112250779A CN 202011165744 A CN202011165744 A CN 202011165744A CN 112250779 A CN112250779 A CN 112250779A
- Authority
- CN
- China
- Prior art keywords
- microspheres
- polystyrene microsphere
- seeds
- reaction
- rare earth
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
- C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F112/06—Hydrocarbons
- C08F112/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
- C08F8/24—Haloalkylation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
-
- 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
- C09D11/50—Sympathetic, colour changing or similar inks
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention discloses a photo-induced color developing microsphere, a preparation method and application thereof, and relates to the technical field of rare earth anti-counterfeiting ink. The method takes styrene as a raw material to prepare polystyrene microsphere seeds, the polystyrene microsphere seeds are subjected to surface modification to enable the surfaces of the microspheres to have amino/carboxyl, and the rare earth ions are introduced to the surfaces of the microspheres by virtue of the coordination of the amino/carboxyl and the rare earth ions, so that the problem of precipitation and delamination of the conventional anti-counterfeiting ink is solved. The preparation method of the photo-induced color developing microspheres provided by the invention can obtain the non-toxic and harmless photo-induced color developing microspheres with high fluorescence, stable property, good glossiness and good printing effect. The preparation method has the advantages of simple and efficient synthesis process, cheap and easily-obtained raw materials, reduction in production cost, no pollution to the environment and high market application value.
Description
Technical Field
The invention relates to the technical field of rare earth anti-counterfeiting ink, in particular to a photo-induced color developing microsphere, a preparation method and application.
Background
In 1950, Dame and company Ltd used fluorescent pigments for the first time in inks to form practical products. In recent years, with intensive research on organic fluorescent dyes, compounds such as coumarins, naphthalimide derivatives, impoundments, xanthenes, ketones, and thioxanthones have been found to have photosensitizing effects. Organic anti-counterfeiting fluorescent ink prepared by Zhangwen officer and the like of Beijing printing academy by utilizing synthetic fluorescent agent 2- (4-methoxyphenyl) -3, 1-benzoxazole-4 ketone can generate strong blue fluorescence under the irradiation of ultraviolet light, and can be used for anti-counterfeiting printing. Yangjiang and the like utilize organic fluorescent materials such as 2-hydroxy-4-methoxybenzophenone, fluorescent whitening agent and the like and ink binders to develop the gravure anti-counterfeiting ink for plastics with colors of red, yellow, light blue and the like which is pioneered at home at that time.
The interest in sensitized emission of rare earth complexes was in the fortieth years of the last century, after which research on the use of rare earth complexes began to grow. The Tianjun and the like of applied chemistry institute of Jiangxi academy of sciences synthesize Eu (TTA)3Phen、Eu(Y)(TTA)3Phen rare earth complex phosphor using fluorescent inert ion Y to Eu (TTA)3Phen performs fluorescence enhancement, and the fluorescent powder, a solvent, a pigment, an ink base material and the like are ground to prepare the rare earth ultraviolet fluorescent anti-counterfeiting ink which is applied to printing of high-grade cigarette packaging boxes. Rare earth fluorescent ink is synthesized by using rare earth metal complexes to prepare fluorescent powder and organic solvent type ink binders. The Wangzhengxiang of the university of China utilizes an in-situ synthesis technology to prepare a corresponding fluorescent agent with good dispersibility in a bisphenol epoxy acrylic acid substrate, and the fluorescent agent is successfully applied to photocuring fluorescent anti-counterfeiting ink to prepare the environment-friendly photocuring fluorescent anti-counterfeiting ink. Zhang Yixiang of the university of Sian rational theory synthesizes a novel light-cured fluorescent anti-counterfeiting ink by using a rare earth complex and a green environment-friendly light-cured binder. Lanzhou university Li Xiang et al uses carbon quantum dots as a substrateThe lanthanide series nano composite material is combined with an amide type beta-diketone lanthanide series complex through coordination, a novel lanthanide series intelligent nano composite material is constructed, the nano composite material is used as fluorescent ink, and information can be stored and encrypted through an ink-jet printing technology.
The existing rare earth anti-counterfeiting ink is prepared by directly dispersing synthesized rare earth complex powder into an ink binder, however, the rare earth anti-counterfeiting ink mainly has the following defects: firstly, the cost of the rare earth complex in the common anti-counterfeiting ink prepared at present is slightly higher, and the usage amount is large, so that the anti-counterfeiting ink is not economical and environment-friendly; secondly, due to the process and cost, the requirement of the particle size distribution of the polymer resin material used in the prior anti-counterfeiting ink is not strict, namely the particle size distribution is wider, so that the prepared ink has poor performance. And thirdly, the rare earth complex solid has poor dispersibility in the ink vehicle, and the prepared ink has rare earth complex precipitation delamination, so that the fluidity and stability of the ink are reduced, printing cracks and concave-convex parts are generated, and the processing and storage are not facilitated. And fourthly, the use requirements of various printing processes (offset printing, silk-screen printing and the like) cannot be met.
Disclosure of Invention
The invention aims to solve the technical problems of defects in the background technology and provides a rare earth composite photo-induced color developing microsphere which is applied to anti-counterfeiting ink.
In order to solve the above problems, the present invention proposes the following technical solutions:
in a first aspect, the present invention provides a method for preparing a photochromic microsphere, comprising the following steps:
preparing polystyrene microsphere seeds:
under the protection of nitrogen, adding azodiisobutyronitrile into styrene in advance, and dissolving uniformly to obtain a styrene solution; dissolving polyvinylpyrrolidone in ethanol to obtain polyvinylpyrrolidone ethanol solution, heating the polyvinylpyrrolidone ethanol solution to 65-75 ℃ under the protection of nitrogen, slowly dropping styrene solution into the polyvinylpyrrolidone ethanol solution after the temperature is stable, and stirring for reaction; after the reaction is finished, washing and drying the reaction product to obtain polystyrene microsphere seeds; wherein the mass ratio of the azodiisobutyronitrile to the styrene is 0.1-1: 100; the mass ratio of the polyvinylpyrrolidone to the styrene is 1-10: 100; the solid content of styrene in ethanol is 30-60%;
chloromethylation of polystyrene microsphere seeds:
under the protection of nitrogen, uniformly dispersing the polystyrene microsphere seeds in dichloromethane, stirring for 0.5-2h at room temperature, fully swelling, and cooling to 0 ℃; adding chloromethyl ether and SnCl4The mixed solution of (1); keeping the temperature at 0 ℃ and continuing stirring for 25-60min, then stirring at room temperature for reaction for 4-12h, and washing and drying the product for later use after the reaction is completed; wherein the mass ratio of the chloromethyl ether to the polystyrene microsphere seeds is 0.1-1: 1;
preparation of amino modified polystyrene microspheres:
under the protection of nitrogen, uniformly dispersing chloromethylated polystyrene microsphere seeds in ethanol, adding an amino modifier, heating to 70-90 ℃, stirring for reaction for 4-12h, and washing and drying a product after complete reaction to obtain amino modified polystyrene microspheres; wherein the mass ratio of the amino modifier to the chloromethylated polystyrene microsphere seeds is 1-10: 100;
preparation of carboxyl modified polystyrene microspheres:
under the protection of nitrogen, uniformly dispersing chloromethylated polystyrene microsphere seeds in anhydrous tetrahydrofuran, adding magnesium chips, stirring and reacting for 4-12h at room temperature, introducing carbon dioxide to continue reacting for 4-12h, adding dilute hydrochloric acid to continue reacting for 4-12h, washing and drying a product after complete reaction to obtain carboxyl modified polystyrene microspheres; wherein the mass ratio of the magnesium chips to the chloromethylated polystyrene microsphere seeds is 1-15: 100;
preparing the rare earth fluorescent particle coated modified polystyrene microsphere:
uniformly dispersing amino modified polystyrene microspheres and/or carboxyl modified polystyrene microspheres in deionized water, slowly adding rare earth ions into the deionized water, stirring and reacting for 1-6 hours at 50-70 ℃, filtering after the reaction is finished to obtain a product, washing and drying to obtain rare earth fluorescent particles coated modified polystyrene microspheres; wherein the mass ratio of the rare earth ions to the amino modified polystyrene microspheres and/or the carboxyl modified polystyrene microspheres is 5-20: 100.
The further technical scheme is that in the preparation step of the polystyrene microsphere seeds, the dripping time is 4-12h, the reaction is carried out after the dripping is finished, and the reaction time is 12-48 h.
The further technical scheme is that in the preparation step of the polystyrene microsphere seeds, the dropping speed of the styrene solution is 0.1-0.5 ml/min.
The further technical scheme is that in the preparation step of the polystyrene microsphere seed, the stirring speed is 75-150 rpm.
The further technical scheme is that in the step of chloromethylation of the polystyrene microsphere seeds, the rotation speed in the swelling process is 180-300 rpm.
The further technical scheme is that in the chloromethylation step of the polystyrene microsphere seeds, SnCl is adopted4The mass ratio of the methyl chloride ether to the methyl chloride ether is 0.1-1: 1.
The further technical scheme is that the amino modifier is selected from triethylamine and trimethylamine.
The further technical scheme is that the rare earth ions are selected from europium acetate, lanthanum vanadate and yttrium nitrate.
In a second aspect, the present invention provides a photochromic microsphere, which is prepared by the preparation method of the photochromic microsphere of the first aspect.
The invention also provides application of the photochromic microspheres in anti-counterfeiting ink.
Compared with the prior art, the invention can achieve the following technical effects:
the method takes styrene as a raw material to prepare polystyrene microsphere seeds, the polystyrene microsphere seeds are subjected to surface modification to enable the surfaces of the microspheres to have amino/carboxyl, and the rare earth ions are introduced to the surfaces of the microspheres by virtue of the coordination of the amino/carboxyl and the rare earth ions, so that the problem of precipitation and delamination of the conventional anti-counterfeiting ink is solved. The preparation method of the photo-induced color developing microspheres provided by the invention can obtain the non-toxic and harmless photo-induced color developing microspheres with good monodispersity, uniform particle size, high fluorescence, stable property, good glossiness and good printing effect. The preparation method has the advantages of simple and efficient synthesis process, cheap and easily-obtained raw materials, reduction in production cost, no pollution to the environment and high market application value.
In addition, the preparation method of the photo-induced color developing microspheres provided by the invention can achieve the effect of controlling the size precision and viscosity of the microspheres by modifying and adjusting the carboxyl/amino groups on the surfaces of the microspheres and matching with process parameters, and avoids the problems of difficult printing, poor storage stability, poor fluidity and the like caused by closed drying while keeping the package and luster of the rare earth particles; the particle size of the polystyrene microsphere can be accurately controlled to be 1-10 mu m, the particle size distribution is uniform, and the polystyrene microsphere can be applied to anti-counterfeiting printing ink and greatly improve the performance of the printing ink.
The photochromic microspheres provided by the invention utilize the microsphere technology to load photosensitive rare earth ions on the surfaces of the microspheres, thereby not only improving the performance of the ink, but also reducing the production cost, reducing the pollution to the environment, having larger market potential and generating good social benefits.
Detailed Description
The technical solutions in the examples will be clearly and completely described below. It is apparent that the embodiments to be described below are only a part of the embodiments of the present invention, and not all of them. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Terms and definitions
Monodispersity: the method refers to that a certain parameter of a substance has uniform property (the shape and the size of the modified polystyrene microsphere wrapped by the rare earth fluorescent particles are very uniform).
Optically variable ink: also known as optically variable inks and chameleons, the color blocks of prints exhibit a pair of colors, for example: red-green, green-blue, gold-silver, etc. The anti-counterfeiting paper is seen from front or side under white light, two different colors are presented along with the change of the visual angle of human eyes, the light variation characteristic is strong, the color difference change is large, the characteristic is obvious, the anti-counterfeiting paper can be identified without any instrument and equipment, the color angle effect cannot be copied by any high-definition scanner, color copier and other equipment, the printing characteristic cannot be imitated by any other printing ink and printing mode, the anti-counterfeiting reliability is extremely high, and therefore the anti-counterfeiting paper is appointed by a plurality of countries in the world to be used for anti-counterfeiting of currency and securities with the strictest requirements and the largest difficulty, and some famous domestic manufacturers are also used for package anti-counterfeiting.
Viscosity: is a measure of the ability of the binder molecules to interact with each other to hinder relative movement between molecules. Viscosity is essentially a manifestation of intermolecular attraction when liquid materials flow. Such an attractive force is related not only to the magnitude of the relative molecular mass but also to the molecular structure and the electrostatic force between molecules. The bonding material has proper viscosity, influences the fineness of the rolled pigment when the viscosity is low, influences the transferability and stability of the ink after the ink is prepared, and the like. The viscosity of the binder is a main factor for determining the viscosity of the ink, and is directly related to the rheological property and the printability of the ink.
Example 1
Preparing polystyrene microsphere seeds:
2.7g of polyvinylpyrrolidone was taken and added to the flask and dissolved in 100g of ethanol to form a polyvinylpyrrolidone ethanol solution. Under the protection of nitrogen, controlling the stirring speed at 90rpm, raising the temperature to 70 ℃ for stabilization, then dissolving 0.27g of azobisisobutyronitrile into 45g of styrene, after the temperature is stabilized, dropwise adding into a flask at the speed of 0.18ml/min for about 5h, reacting at 70 ℃ for 24h, washing the product with ethanol for 3 times after the reaction is finished, washing in deionized water for 3 times, and drying in a vacuum oven at 60 ℃ after the washing to obtain the polystyrene microsphere seed for later use.
Preparing amino modified polystyrene microspheres:
dispersing 10g of the polystyrene microsphere seeds in 50ml of dichloromethane, stirring at the room temperature for 1h at the stirring speed of 200rpm, introducing nitrogen for protection, and uniformly dispersing and swelling the polystyrene microsphere seeds in the dichloromethane at the swelling speed of 200 rpm; cooling to 0 ℃ after swelling is finished;to this was slowly added 8ml of chloromethyl ether and 1.5ml of SnCl4The mixed solution of (1); keeping the temperature at 0 ℃ and continuing stirring for 30 min; stirring for 6h at room temperature to chloromethylate the polystyrene microsphere seeds; after the reaction is completed, washing with water, 5% HCl, water, THF (tetrahydrofuran), ethanol and acetone in sequence; and (3) after washing, placing the washed polystyrene microspheres in a vacuum oven at 50 ℃ for drying to obtain chloromethylated polystyrene microsphere seeds.
Uniformly dispersing 10g of the chloromethylated polystyrene microsphere seeds in 50ml of ethanol, adding triethylamine (the mass ratio of triethylamine to the chloromethylated polystyrene microsphere seeds is 5: 100), heating to 80 ℃, stirring for reaction for 12 hours, after the reaction is completed, washing the product with water, ethanol and acetone in sequence, and drying in a vacuum oven at 50 ℃ for 24 hours to obtain the amino modified polystyrene microsphere.
Preparation of carboxyl modified polystyrene microspheres:
dispersing 10g of the polystyrene microsphere seeds in 50ml of dichloromethane, stirring at the room temperature for 1h at the stirring speed of 200rpm, introducing nitrogen for protection, and uniformly dispersing and swelling the polystyrene microsphere seeds in the dichloromethane at the swelling speed of 200 rpm; cooling to 0 ℃ after swelling is finished; to this was slowly added 8ml of chloromethyl ether and 1.5ml of SnCl4The mixed solution of (1); keeping the temperature at 0 ℃ and continuing stirring for 30 min; stirring for 6h at room temperature to chloromethylate the polystyrene microsphere seeds; after the reaction is completed, washing with water, 5% HCl, water, THF (tetrahydrofuran), ethanol and acetone in sequence; and (3) after washing, placing the washed polystyrene microspheres in a vacuum oven at 50 ℃ for drying to obtain chloromethylated polystyrene microsphere seeds.
Uniformly dispersing 10g of the chloromethylated polystyrene microsphere seeds in 50mL of freshly distilled anhydrous tetrahydrofuran, adding 1g of magnesium chips (the mass ratio of the magnesium chips to the chloromethylated polystyrene microsphere seeds is 10:100), introducing nitrogen and absolute oxygen in the whole process, stirring for 6 hours at room temperature, introducing carbon dioxide, continuously stirring for reaction for 6 hours, adding 50mL of 10% diluted hydrochloric acid, continuously stirring for reaction for 6 hours, washing the product with deionized water after the reaction is completed, and performing vacuum drying for 24 hours at 60 ℃ to obtain the carboxyl modified polystyrene microspheres.
Preparing rare earth fluorescent particle coated modified polystyrene microspheres:
uniformly dispersing 10g of amino modified polystyrene microspheres and/or carboxyl modified polystyrene microspheres in 50ml of deionized water, slowly adding 1g of europium acetate hydrate, heating to 60 ℃, stirring for reaction for 4 hours, after the reaction is finished, carrying out suction filtration on the mixture, cleaning the product with deionized water, and carrying out vacuum drying for 24 hours at 60 ℃.
In the embodiment, styrene is used as a raw material to prepare polystyrene microsphere seeds, the polystyrene microsphere seeds are subjected to surface modification to enable the surfaces of the microspheres to have amino/carboxyl groups, and rare earth ions are introduced to the surfaces of the microspheres by virtue of the coordination effect of the amino/carboxyl groups and the rare earth ions, so that the problem of precipitation and delamination of the existing anti-counterfeiting ink is solved. The preparation method of the photo-induced color developing microspheres provided by the invention can obtain the non-toxic and harmless photo-induced color developing microspheres with high fluorescence, stable property, good glossiness and good printing effect. The preparation method has the advantages of simple and efficient synthesis process, cheap and easily-obtained raw materials, reduction in production cost, no pollution to the environment and high market application value.
In other embodiments, in the step of preparing the polystyrene microsphere seed, the mass ratio of the azobisisobutyronitrile to the styrene is 0.1-1: 100.
For example, in one embodiment, the mass ratio of azobisisobutyronitrile to styrene is 0.4: 100.
In one embodiment, the mass ratio of azobisisobutyronitrile to styrene is 0.8: 100.
In other embodiments, in the step of preparing the polystyrene microsphere seed, the mass ratio of the polyvinylpyrrolidone to the styrene is 1-10: 100.
For example, in one embodiment, the mass ratio of polyvinylpyrrolidone to styrene is 3: 100.
In one embodiment, the mass ratio of polyvinylpyrrolidone to styrene is 7: 100.
In one embodiment, the mass ratio of polyvinylpyrrolidone to styrene is 9: 100.
In other embodiments, the styrene content in ethanol during the step of preparing the polystyrene microsphere seeds is 30-60%.
For example, in one embodiment, the styrene has a solids content of 40% in ethanol.
In one embodiment, the styrene has a solids content of 50% in ethanol.
In other embodiments, in the step of preparing the polystyrene microsphere seeds, the dropping time is 4-12h, and the reaction is carried out after the dropping is finished, wherein the reaction time is 12-48 h.
For example, in one embodiment, in the step of preparing the polystyrene microsphere seeds, the dropping speed of the styrene solution is 0.5ml/min, the dropping time is 6 hours, and the reaction is carried out after the dropping is finished, and the reaction time is 46 hours.
In one embodiment, in the step of preparing the polystyrene microsphere seeds, the dropping speed of the styrene solution is 0.3ml/min, the dropping time is 9 hours, and the reaction is carried out after the dropping is finished, wherein the reaction time is 22 hours.
In one embodiment, in the step of preparing the polystyrene microsphere seeds, the dropping speed of the styrene solution is 0.12ml/min, the dropping time is 11 hours, and the reaction is carried out after the dropping is finished, wherein the reaction time is 36 hours.
In other embodiments, in the step of preparing the polystyrene microsphere seeds, the stirring speed is 75-150 rpm.
For example, in one embodiment, in the step of preparing the polystyrene microsphere seeds, the stirring speed is 80 rpm.
In one embodiment, in the step of preparing the polystyrene microsphere seeds, the stirring speed is 100 rpm.
In one embodiment, in the step of preparing the polystyrene microsphere seeds, the stirring speed is 120 rpm.
In other embodiments, in the step of chloromethylation of the polystyrene microsphere seeds, the rotation speed of the swelling process is 180-300 rpm; the mass ratio of the chloromethyl ether to the polystyrene microsphere seed is 0.1-1: 1.
For example, in one embodiment, in the step of chloromethylation of the polystyrene microsphere seeds, the rotation speed of the swelling process is 230 rpm; the mass ratio of chloromethyl ether to polystyrene microsphere seed is 0.4: 1.
In one embodiment, in the step of chloromethylation of the polystyrene microsphere seeds, the rotation speed of the swelling process is 250 rpm; the mass ratio of chloromethyl ether to polystyrene microsphere seed is 0.6: 1.
In one embodiment, in the step of chloromethylation of the polystyrene microsphere seeds, the rotation speed of the swelling process is 290 rpm; the mass ratio of chloromethyl ether to polystyrene microsphere seed is 0.9: 1.
In other embodiments, in the step of preparing the amino-modified polystyrene microsphere, the mass ratio of the amino-modifying agent to the chloromethylated polystyrene microsphere seed is 1-10: 100.
For example, in one embodiment, in the step of preparing the amino-modified polystyrene microsphere, the mass ratio of the amino-modifying agent to the chloromethylated polystyrene microsphere seed is 2: 100.
In one embodiment, in the step of preparing the amino-modified polystyrene microsphere, the mass ratio of the amino-modifying agent to the chloromethylated polystyrene microsphere seed is 5: 100.
In one embodiment, in the step of preparing the amino-modified polystyrene microsphere, the mass ratio of the amino-modifying agent to the chloromethylated polystyrene microsphere seed is 8: 100.
In one embodiment, the amino modifier is selected from triethylamine.
In other embodiments, in the step of preparing the carboxyl-modified polystyrene microspheres, the mass ratio of the magnesium chips to the chloromethylated polystyrene microsphere seeds is 1-15: 100.
For example, in one embodiment, the mass ratio of magnesium turnings to chloromethylated polystyrene microsphere seeds is 2: 100.
In one example, the mass ratio of magnesium turnings to chloromethylated polystyrene microsphere seeds is 5: 100.
In one example, the mass ratio of magnesium turnings to chloromethylated polystyrene microsphere seeds is 7: 100.
In one example, the mass ratio of magnesium turnings to chloromethylated polystyrene microsphere seeds is 10: 100.
In one example, the mass ratio of magnesium turnings to chloromethylated polystyrene microsphere seeds is 13: 100.
In one embodiment, the rare earth ions are selected from europium acetate hydrate and lanthanum vanadate.
In one embodiment, the rare earth ions are selected from yttrium nitrate and lanthanum vanadate.
In one embodiment, the rare earth ions are selected from a mixture of europium acetate hydrate, yttrium nitrate, and lanthanum vanadate.
In other embodiments, the mass ratio of the rare earth ions to the amino-modified polystyrene microspheres and/or the carboxyl-modified polystyrene microspheres is 5-20: 100.
For example, in one embodiment, the mass ratio of rare earth ions to amino-modified polystyrene microspheres and/or carboxy-modified polystyrene microspheres is 6: 100.
In one embodiment, the mass ratio of the rare earth ions to the amino-modified polystyrene microspheres and/or the carboxyl-modified polystyrene microspheres is 10: 100.
In one embodiment, the mass ratio of the rare earth ions to the carboxyl-modified polystyrene microspheres and/or the carboxyl-modified polystyrene microspheres is 17: 100.
In one embodiment, the mass ratio of the rare earth ions to the amino-modified polystyrene microspheres and/or the carboxyl-modified polystyrene microspheres is 15: 100.
In one embodiment, the mass ratio of the rare earth ions to the amino-modified polystyrene microspheres and/or the carboxyl-modified polystyrene microspheres is 20: 100; wherein, the selection of the amino modified polystyrene microsphere and/or the carboxyl modified polystyrene microsphere is determined according to the property of rare earth ions.
That is, in the embodiment of the present invention, a person skilled in the art can select the amount of the amino-modified polystyrene microspheres and/or the carboxyl-modified polystyrene microspheres according to the property of the rare earth ions.
In the above embodiments, the descriptions of the respective embodiments have respective emphasis, and for parts that are not described in detail in a certain embodiment, reference may be made to related descriptions of other embodiments.
While the invention has been described with reference to specific embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. A preparation method of a photochromic microsphere is characterized by comprising the following steps:
preparing polystyrene microsphere seeds:
under the protection of nitrogen, adding azodiisobutyronitrile into styrene in advance, and dissolving uniformly to obtain a styrene solution; dissolving polyvinylpyrrolidone in ethanol to obtain polyvinylpyrrolidone ethanol solution, heating the polyvinylpyrrolidone ethanol solution to 65-75 ℃ under the protection of nitrogen, slowly dropping styrene solution into the polyvinylpyrrolidone ethanol solution after the temperature is stable, and stirring for reaction; after the reaction is finished, washing and drying the reaction product to obtain polystyrene microsphere seeds; wherein the mass ratio of the azodiisobutyronitrile to the styrene is 0.1-1: 100; the mass ratio of the polyvinylpyrrolidone to the styrene is 1-10: 100; the solid content of styrene in ethanol is 30-60%;
chloromethylation of polystyrene microsphere seeds:
under the protection of nitrogen, uniformly dispersing the polystyrene microsphere seeds in dichloromethane, stirring for 0.5-2h at room temperature, fully swelling, and cooling to 0 ℃; adding chloromethyl ether and SnCl4The mixed solution of (1); keeping the temperature at 0 ℃ and continuing stirring for 25-60min, then stirring at room temperature for reaction for 4-12h, and washing and drying the product for later use after the reaction is completed; wherein the mass ratio of the chloromethyl ether to the polystyrene microsphere seeds is 0.1-1: 1;
preparation of amino modified polystyrene microspheres:
under the protection of nitrogen, uniformly dispersing chloromethylated polystyrene microsphere seeds in ethanol, adding an amino modifier, heating to 70-90 ℃, stirring for reaction for 4-12h, and washing and drying a product after complete reaction to obtain amino modified polystyrene microspheres; wherein the mass ratio of the amino modifier to the chloromethylated polystyrene microsphere seeds is 1-10: 100;
preparation of carboxyl modified polystyrene microspheres:
under the protection of nitrogen, uniformly dispersing chloromethylated polystyrene microsphere seeds in anhydrous tetrahydrofuran, adding magnesium chips, stirring and reacting for 4-12h at room temperature, introducing carbon dioxide to continue reacting for 4-12h, adding dilute hydrochloric acid to continue reacting for 4-12h, washing and drying a product after complete reaction to obtain carboxyl modified polystyrene microspheres; wherein the mass ratio of the magnesium chips to the chloromethylated polystyrene microsphere seeds is 1-15: 100;
preparing the rare earth fluorescent particle coated modified polystyrene microsphere:
uniformly dispersing amino modified polystyrene microspheres and/or carboxyl modified polystyrene microspheres in deionized water, slowly adding rare earth ions into the deionized water, stirring and reacting for 1-6 hours at 50-70 ℃, filtering after the reaction is finished to obtain a product, washing and drying to obtain rare earth fluorescent particles coated modified polystyrene microspheres; wherein the mass ratio of the rare earth ions to the amino modified polystyrene microspheres and/or the carboxyl modified polystyrene microspheres is 5-20: 100.
2. The method for preparing the photochromic microspheres according to claim 1, wherein in the step of preparing the polystyrene microsphere seeds, the dripping time is 4-12 hours, and the reaction is carried out after the dripping is finished, wherein the reaction time is 12-48 hours.
3. The method for preparing microspheres according to claim 2, wherein the polystyrene microsphere seeds are prepared by dropping a styrene solution at a rate of 0.1-0.5 ml/min.
4. The method for preparing microspheres according to claim 1, wherein the step of preparing the seeds of polystyrene microspheres is carried out at a stirring speed of 75-150 rpm.
5. The method for preparing microspheres according to claim 1, wherein the rotation speed of the swelling process in the chloromethylation step of the polystyrene microsphere seeds is 180-300 rpm.
6. The method of claim 1, wherein during the chloromethylation step of the polystyrene microsphere seed, SnCl is used4The mass ratio of the methyl chloride ether to the methyl chloride ether is 0.1-1: 1.
7. The method of claim 1, wherein the amino modifier is at least one selected from triethylamine and trimethylamine.
8. The method of claim 1, wherein the rare earth ions are at least one selected from europium acetate, lanthanum vanadate, and yttrium nitrate.
9. A photochromic microsphere produced by the method for producing a photochromic microsphere according to any one of claims 1 to 8.
10. Use of the photo-chromic microspheres of claim 9 in security inks.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011165744.0A CN112250779B (en) | 2020-10-27 | 2020-10-27 | Photochromic microspheres, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011165744.0A CN112250779B (en) | 2020-10-27 | 2020-10-27 | Photochromic microspheres, preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112250779A true CN112250779A (en) | 2021-01-22 |
| CN112250779B CN112250779B (en) | 2022-06-10 |
Family
ID=74262181
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011165744.0A Active CN112250779B (en) | 2020-10-27 | 2020-10-27 | Photochromic microspheres, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112250779B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB810025A (en) * | 1955-11-21 | 1959-03-11 | Ici Ltd | New polymeric materials |
| GB856307A (en) * | 1957-12-11 | 1960-12-14 | Ici Ltd | Oil-modified alkyd resins |
| CN1724584A (en) * | 2005-07-14 | 2006-01-25 | 西南师范大学 | Chloromethylated chloromethylated oligostyryl phosphonic acid-phosphate and its use |
| CN103788264A (en) * | 2014-01-24 | 2014-05-14 | 中南大学 | Grafted acylamino hydroximic acid polymer and preparation method thereof |
| CN104558383A (en) * | 2015-01-06 | 2015-04-29 | 湖北鼎龙化学股份有限公司 | Fluorescent complex containing carboxylic acid type high polymer and rare earth, preparation method of fluorescent complex, fluorescent chemical carbon powder and preparation method of fluorescent chemical carbon powder |
| CN108485649A (en) * | 2018-04-25 | 2018-09-04 | 深圳市裕同包装科技股份有限公司 | A kind of fast preparation method of rare earth down-conversion fluorescent microballoon |
| CN108579633A (en) * | 2018-03-29 | 2018-09-28 | 山东大学 | A kind of preparation method of rare-earth nanometer particles/polystyrene complex microsphere |
-
2020
- 2020-10-27 CN CN202011165744.0A patent/CN112250779B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB810025A (en) * | 1955-11-21 | 1959-03-11 | Ici Ltd | New polymeric materials |
| GB856307A (en) * | 1957-12-11 | 1960-12-14 | Ici Ltd | Oil-modified alkyd resins |
| CN1724584A (en) * | 2005-07-14 | 2006-01-25 | 西南师范大学 | Chloromethylated chloromethylated oligostyryl phosphonic acid-phosphate and its use |
| CN103788264A (en) * | 2014-01-24 | 2014-05-14 | 中南大学 | Grafted acylamino hydroximic acid polymer and preparation method thereof |
| CN104558383A (en) * | 2015-01-06 | 2015-04-29 | 湖北鼎龙化学股份有限公司 | Fluorescent complex containing carboxylic acid type high polymer and rare earth, preparation method of fluorescent complex, fluorescent chemical carbon powder and preparation method of fluorescent chemical carbon powder |
| CN108579633A (en) * | 2018-03-29 | 2018-09-28 | 山东大学 | A kind of preparation method of rare-earth nanometer particles/polystyrene complex microsphere |
| CN108485649A (en) * | 2018-04-25 | 2018-09-04 | 深圳市裕同包装科技股份有限公司 | A kind of fast preparation method of rare earth down-conversion fluorescent microballoon |
Non-Patent Citations (6)
| Title |
|---|
| LUIGI ANGIOLINI ET AL.: "Tri-n-butyltin carboxylate derivatives of para-substituted phenyl-ethanoic acids: synthesis, characterization and X-ray structure determination", 《JOURNAL OF ORGANOMETALLIC CHEMISTRY》 * |
| N.K.马瑟等著，李弘等译: "《聚合物在有机化学中的应用》", 31 October 1986, 化学工业出版社 * |
| 土田英俊著，万国祥等译: "《高分子科学》", 30 June 1983, 人民教育出版社 * |
| 夏雪伟等: "以对氯甲基苯甲酸引发苯乙烯ATRP聚合及聚合物与稀土金属配位研究", 《高校化学工程学报》 * |
| 彭超: "含稀土配合物的荧光编码聚苯乙烯微球的制备与表征", 《中国优秀硕士学位论文全文数据库工程科技第I辑》 * |
| 王鲁霞等: "聚苯乙烯基螯合材料的制备及应用进展", 《化工新型材料》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112250779B (en) | 2022-06-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6739071B2 (en) | Membranes and articles containing core-shell particles | |
| JP4334204B2 (en) | High-luminance and high-saturation iris pigment and method for producing the same | |
| CN101410462B (en) | Bright pigment with gold tone, and cosmetic, paint, ink or resin composition containing the same | |
| KR101541009B1 (en) | Colored glazed pigments using natural dye and method of manufacturing the same | |
| CN105907177B (en) | A kind of inkjet printing tempered glass ink and preparation method thereof | |
| CN101327479A (en) | Method for preparing composite bandgap colloidal photonic crystal film using inkjet printing method | |
| EP1707599A1 (en) | Colored bright pigment | |
| JPH07268240A (en) | Carbon containing pigment | |
| CN112250779B (en) | Photochromic microspheres, preparation method and application | |
| KR101526540B1 (en) | Method of manufacturing of iron oxide based black glazed pigments | |
| Tao et al. | Tetraphenylbenzene-modified photonic crystal structure colour coating on fabric substrates for dual-mode anticounterfeiting | |
| EP1697468B1 (en) | Colored metal pigments, method for the production thereof, use of the colored metal pigments in cosmetics, and cosmetic containing these | |
| JPS59109561A (en) | Light stable yellow composite pigment and manufacture | |
| CN112048218A (en) | Photo-induced color development anti-counterfeiting water-based ink and preparation method thereof | |
| CN108559312B (en) | Preparation method of cobalt coloring mica pearlescent pigment | |
| CN108276806B (en) | Containing rutile and anatase TiO2Layered pearlescent pigments and method for the production thereof | |
| JP3911315B2 (en) | High saturation orange pearl pigment | |
| JP6853352B2 (en) | Black pearl luster pigment using natural charcoal and its manufacturing method | |
| CN102174276B (en) | Method for preparing cerium-doped hollow nano titanium dioxide yellow pigment for electronic paper | |
| CN103694746B (en) | A kind of preparation method of multifunctional magnetic synthetic mica pearlescent pigment | |
| CN113072822B (en) | A kind of preparation method of blue pearlescent pigment based on ultramarine pigment | |
| CN104372712A (en) | Metalized grinding paper with optical variability effect and preparation method thereof | |
| CN114181694A (en) | A kind of red fluorescent electrophoretic particle for electronic paper and preparation method and application thereof | |
| JPH07258585A (en) | Water-based coating composition and variable-color coating film | |
| CN108003664B (en) | Infrared-absorbing photo-thermal effect pearlescent pigment and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |