CN113563870B - Temperature-sensitive organic aggregation luminescent material and preparation method thereof - Google Patents
Temperature-sensitive organic aggregation luminescent material and preparation method thereof Download PDFInfo
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- 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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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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Abstract
The temperature-sensitive organic aggregation luminescent material is prepared by dissolving TPE in an organic solvent to prepare nano emulsion and then freeze-drying the nano emulsion. The invention can realize the change of color and brightness along with the temperature, and provides a good material for manufacturing the temperature sensor.
Description
Technical Field
The invention belongs to the technical field of organic luminescent materials, and particularly relates to a temperature-sensitive organic aggregation luminescent material and a preparation method thereof.
Background
A new class of organic light emitting materials with Aggregation Induced Emission (AIE) characteristics, referred to as AIE molecules. AIE does not emit light in a dissolved state, but the movement in molecules is limited due to the formation of pi-pi accumulation during aggregation, so that electrons in an excited state return to a ground state by means of radiative transition, and fluorescence is generated in the transition process. During the past 10 years, researchers have prepared various types of AIE-based fluorescent materials for applications in the fields of chemosensing, biosensing, cellular imaging, thermochromic and piezochromic sensing.
Nanoemulsion (nano emulsion), also called microemulsion (micro emulsion), is a thermodynamically stable, isotropic, transparent or translucent homogeneous dispersion system formed by oily droplets (500 nm) coated with a surfactant dispersed in water. The emulsion stratification caused by the density difference of oil phase and water phase disappears because of the small particle size. The nano emulsion can be widely applied immediately after appearing, and is mainly applied to the fields of drug targeted delivery, cosmetics, food and the like.
In the existing organic temperature-sensitive luminescent material, due to the limitation of materials, the transparency is poor, the temperature change and the color change response are not matched, and the luminous efficiency is low. The AIE under the aggregation state is coated by the nano liquid drops to obtain the temperature-sensitive fluorescence controllable AIE luminescent material which can be used in the fields of trademark anti-counterfeiting, temperature sensing and the like.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a temperature-sensitive organic aggregation luminescent material and a preparation method thereof, wherein the temperature-sensitive organic aggregation luminescent material has good transmittance, can realize the change of color and brightness along with temperature, and provides a good material for manufacturing a temperature sensor.
In order to achieve the purpose, the invention adopts the technical scheme that:
the temperature-sensitive organic aggregation luminescent material is prepared by dissolving TPE in an organic solvent to prepare nano emulsion and then freeze-drying the nano emulsion.
A preparation method of a temperature-sensitive organic aggregation luminescent material comprises the following steps;
(1) Dissolving TPE into medium-chain glycerol or medium-chain triglyceride organic solution at 70 ℃;
(2) Dissolving acrylic resin monomers, the organic solution dissolved in the step 1, a photoinitiator and modified castor oil mutually to obtain an oil phase solution;
(3) At room temperature, adding deionized water into the oil phase solution obtained in the step (2) in a certain proportion, and dispersing by utilizing mechanical stirring, homogeneous emulsification, ultrasonic emulsification or microfluidization emulsification to prepare emulsion;
(4) Irradiating and curing the emulsion obtained in the step (3) by using an ultraviolet crosslinking instrument at room temperature;
(5) Dialyzing the emulsion after photocuring in deionized water for 5 days;
(6) Freeze-drying the dialyzed emulsion, and collecting a product;
the solubility of TPE in medium-chain glycerol or medium-chain triglycerides in step (1) is measured in advance.
The acrylic resin monomer in the step (2) is one of 1,6-hexanediol diacrylate (HDDA) and tripropylene glycol diacrylate (TPGDA).
The medium-chain glycerol or medium-chain triglyceride in the step (2) is one of Labrafac CC and Labrafac WL 1349;
the photoinitiator in the step (2) is one of 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxycyclohexyl phenyl ketone and 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-acetone;
the modified castor oil in the step (2) is one of Cremopher EL, cremopher ELP and Cremopher RH 40.
The acrylic resin monomer, the medium-chain glycerol or the medium-chain triglyceride, the photoinitiator and the modified castor oil in the step (2) are mixed according to the ratio of (1-25): (1-30): (0.1-0.9): (3-50) in a mass ratio.
The oil phase solution in the step (3) and deionized water are mixed according to the ratio of (1-3): (2-5) in a mass ratio.
And (4) stirring in the step (3) is vortex stirring, magnetic stirring and microflow emulsification.
In the step (4), the extraction time of the TPE is measured before the UV light is radiated for curing.
The injection speed in the step (4) is 100 mu m/min-2 ml/min.
The output power of the UV light radiation machine in the step (4) is 200W-300W.
The cut-off molecular weight of the dialysis bag in the step (5) is 8000-14000.
The dialysis time in the step (5) is 2 to 10 days;
the treatment time in the step (5) is 10 s-500 s.
The invention has the beneficial effects that:
the invention obtains the heat-sensitive organic aggregation luminescent material and the preparation method thereof. The process uses green and easily-obtained raw materials, and the preparation process is simple; the prepared product is environment-friendly and does not cause secondary pollution.
According to the invention, the solubility change of the TPE at different temperatures is utilized to design the gel capable of realizing color change at different temperatures, so that the application of AIE is widened, and a scheme is provided for designing various temperature sensors.
Drawings
FIG. 1 is a fluorescence absorption spectrum of a nanoemulsion containing TPE.
FIG. 2 is a graph containing a fluorescence intensity spectrum and a real object.
Figure 3 is a schematic of a nanoemulsion DLS containing TPE.
Fig. 4 DLS schematic of lyophilized emulsion.
FIG. 5 is a schematic representation of the gel before and after heating under a 365nm UV lamp.
Detailed Description
The present invention will be described in further detail with reference to examples.
The preparation method comprises the following steps;
(1) Tetraphenylethylene was dissolved in modified castor oil at 70 ℃.
(2) At the temperature of 25-40 ℃, dissolving acrylic resin monomers, medium-chain glycerol or medium-chain triglyceride, a photoinitiator and modified castor oil mutually to obtain an oil phase solution; the acrylic resin monomer is a monomer forming a polymer organic framework; the medium-chain glycerol or the medium-chain triglyceride is used as a nano-droplet stabilizer, the photoinitiator can initiate acrylic resin monomers to react to form an organic nano-sized polymer, and the modified castor oil is used for stabilizing the nano-emulsion.
(3) At room temperature, adding deionized water into the oil phase solution obtained in the step (1) in a certain proportion, and performing mechanical stirring, homogeneous emulsification, ultrasonic emulsification or microfluidization emulsification to obtain emulsion; after the oil phase and the water phase are mixed, the hydrophobic group of the modified castor oil is positioned on the inner side of the oil phase, and the hydrophilic group is positioned on the outer side of the oil phase, so that the structural stability of the modified castor oil is maintained.
(4) Standing, and performing light radiation curing on the emulsion obtained in the step (3) by using an ultraviolet crosslinking instrument at room temperature; in the process, the nano emulsion is irradiated by ultraviolet rays, and the photoinitiator and the acrylic resin monomer form a polymer nano framework.
(5) Dialyzing the mixed solution prepared in the step (4) by using deionized water to remove the excessive modified castor oil.
(6) And (5) freeze-drying the mixed solution prepared in the step (5) to obtain the thermosensitive fluorescent material.
The propylene resin monomer in the step (2) is one of 1,6-hexanediol diacrylate (HDDA) and tripropylene glycol diacrylate (TPGDA).
The medium-chain glycerol or medium-chain triglyceride in the step (2) is one of Labrafac CC and Labrafac WL 1349;
the photoinitiator in the step (2) is one of 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxycyclohexyl phenyl ketone and 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-acetone;
the modified castor oil in the step (2) is one of Cremopher EL, cremopher ELP and Cremopher RH 40.
The acrylic resin monomer, the medium-chain glycerol or the medium-chain triglyceride, the photoinitiator and the modified castor oil in the step (2) are prepared from (1-25): (1-30): (0.1-0.9): (3-50) in a mass ratio.
The oil phase solution in the step (3) and deionized water are mixed according to the ratio of (1-3): (2-5) in a mass ratio.
And (4) stirring in the step (3) is vortex stirring, magnetic stirring and microflow emulsification.
The radiation curing technology in the step (4) is Ultraviolet (UV) radiation light irradiation curing.
The injection speed in the step (4) is 100 mu m/min-2 ml/min.
The output power of the UV curing machine in the step (4) is 200W-300W.
The cut-off molecular weight of the dialysis bag in the step (5) is 8000-14000.
The dialysis time in the step (5) is 2 to 10 days.
Example 1
TPE is dissolved in Labrafac CC at 70 ℃,5g of propylene resin monomer 1,6-hexanediol diacrylate (HDDA) and 5g of Labrafac CC are mixed uniformly, 4% of 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-acetone photoinitiator is added, and 4g of modified castor oil Cremopher RH 40 is added to prepare an oil phase mixture. And dividing the 14g of oil phase mixture into 7 parts by taking 2g as a component, mixing the oil phase and water according to the mass ratio of 5:3, and performing vortex to prepare the TPE-containing nano emulsion. The nano emulsion is irradiated and solidified by ultraviolet light at the advancing speed of 0.2ml/min by an injection pump to prepare the organic nano body type polymer. Putting the UV-cured substance into a dialysis bag, sealing the dialysis bag, putting the dialysis bag into deionized water, dialyzing for 5 days to remove Cremopher RH 40, and freeze-drying to obtain the polymer gel. And (3) blade-coating the freeze-dried emulsion on tin foil paper to obtain a film with the thickness of 200 um.
Example 2
At 70 ℃, TPE is dissolved in Labrafac CC, 1g of acrylic resin monomer 1,6-hexanediol diacrylate (HDDA) and 1g of Labrafac CC are mixed uniformly, 0.1g of photoinitiator 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-acetone is added, and 10g of modified castor oil Cremopher RH 40 is added to prepare an oil phase mixture. The oil phase mixture is divided into 10 parts, and the oil phase and the water are mixed according to the mass ratio of 1:5 and are swirled to prepare the nano emulsion. The nano emulsion is irradiated and solidified by Ultraviolet (UV) radiation with 10 percent of irradiation intensity at the advancing speed of 100 mu m/min in an injection pump to prepare the nano organic framework emulsion. Putting the UV-cured substance into a dialysis bag with a carrying and remaining molecular weight of 8000, sealing, putting into deionized water, dialyzing for 10 days to remove Cremopher RH 40, and freeze-drying to obtain the gel polymer of the nano organic framework. And (3) blade-coating the freeze-dried emulsion on tin foil paper to obtain a film with the thickness of 150 um.
Example 3
TPE is dissolved in Labrafac WL 1349 at 70 ℃, 25g of acrylic resin monomer tripropylene glycol diacrylate (TPGDA) and 30g of Labrafac WL 1349 are mixed uniformly, 0.9g of photoinitiator 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-acetone is added, and 50g of modified castor oil Cremopher ELP is added to prepare an oil phase mixture. The oil phase mixture is divided into 10 parts, and the oil phase and the water are mixed according to the mass ratio of 3:2 and are swirled to prepare the nano emulsion. The nano emulsion is irradiated and solidified by Ultraviolet (UV) radiation with 100 percent of irradiation intensity at the advancing speed of 2ml/min in an injection pump to prepare the nano organic framework emulsion. Putting the UV-cured substance into a dialysis bag with the carrying and remaining molecular weight of 14000, sealing, putting into deionized water for dialysis for 2 days to remove Cremopher ELP, and performing freeze drying to obtain the gel polymer of the nano organic framework. The freeze-dried emulsion was drawn down onto glass slides to give films of 150um thickness.
As shown in fig. 1: the emulsion has a relatively wide absorption peak around 320nm, which indicates that the emulsion can generate fluorescence under excitation at 320 with high probability.
As shown in fig. 2: when the fluorescence intensity spectrum is excited by ultraviolet 320nm light, green fluorescence overflows at 478nm, so that the TPE is successfully embedded in the nanoparticles, and the nanoparticles can well limit the rotation of benzene rings of TPE molecules to generate fluorescence. And comparing the top right-hand picture with the picture in the dark environment.
As shown in fig. 3: the PDI of the nanoemulsion is 0.19; z-average (d.nm): 37.8, which shows that the nano emulsion is monodisperse and has small particle size of only dozens of nanometers. The homogeneity of the nanoemulsion was very good.
As shown in fig. 4: the nano emulsion containing TPE is not demulsified after being freeze-dried, and PDI is 0.29, which shows that the emulsion can be dispersed after being freeze-dried; z-average (d.nm): 126.7, which shows that the particle size of the emulsion is enlarged after dialysis and freeze-drying.
As shown in fig. 5: the emulsion after freeze-drying can realize the change of fluorescence intensity along with the temperature change under the UV lamp, which shows that TPE can be re-aggregated to be dispersed in nano-particles, makes full use of the basic mechanism of AIE luminescence, and realizes luminescence by limiting the rotation of molecules.
Claims (7)
1. The preparation method of the temperature-sensitive organic aggregation luminescent material is characterized by comprising the following steps;
(1) Dissolving TPE into medium-chain glycerol or medium-chain triglyceride organic solution at 70 ℃;
(2) Dissolving acrylic resin monomers, the organic solution dissolved in the step 1, a photoinitiator and modified castor oil mutually to obtain an oil phase solution;
(3) At room temperature, adding deionized water into the oil phase solution obtained in the step (2) in a certain proportion, and dispersing by utilizing mechanical stirring, homogeneous emulsification, ultrasonic emulsification or microfluidization emulsification to prepare emulsion;
(4) Irradiating and curing the emulsion obtained in the step (3) by using an ultraviolet crosslinking instrument at room temperature;
(5) Dialyzing the emulsion after photocuring in deionized water for 5 days;
(6) Freeze-drying the dialyzed emulsion, and collecting a product;
the material is prepared by dissolving TPE in an organic solvent to prepare nano emulsion and then freeze-drying, the fluorescence intensity of the prepared material has the capability of changing along with the temperature, and the material can be adhered to most objects and has excellent light transmission.
2. The method for preparing a temperature-sensitive organic aggregation luminescent material according to claim 1, wherein the solubility of TPE in medium-chain glycerol or medium-chain triglyceride is measured in advance in the step (1).
3. The method for preparing a temperature-sensitive organic aggregation luminescent material according to claim 1, wherein the acrylic resin monomer in the step (2) is one of 1,6-hexanediol diacrylate (HDDA) and tripropylene glycol diacrylate (TPGDA);
the medium-chain glycerol or medium-chain triglyceride in the step (2) is one of Labrafac CC and Labrafac WL 1349;
the photoinitiator in the step (2) is one of 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxycyclohexyl phenyl ketone and 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-acetone;
the modified castor oil in the step (2) is one of Cremopher EL, cremopher ELP and Cremopher RH 40.
4. The method for preparing the temperature-sensitive organic aggregation luminescent material according to claim 1, wherein the acrylic resin monomer, the medium-chain glycerol or the medium-chain triglyceride, the photoinitiator and the modified castor oil in the step (2) are prepared in the following ratio (1 to 25): (1 to 30): (0.1 to 0.9): (3 to 50) in a mass ratio.
5. The method for preparing a temperature-sensitive organic aggregation luminescent material according to claim 1, wherein the oil phase solution in the step (3) is mixed with deionized water to obtain a mixture (1~3): (2~5) was mixed and stirred in a mass ratio.
6. The method for preparing a temperature-sensitive organic aggregation luminescent material according to claim 1, wherein the stirring in the step (3) is vortex stirring or magnetic stirring.
7. The method for preparing the temperature-sensitive organic aggregation luminescent material according to claim 1, wherein the cut-off molecular weight of a dialysis bag during dialysis in the step (5) is 8000-14000.
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| CN104945537A (en) * | 2015-05-26 | 2015-09-30 | 浙江大学 | Preparation method of water-soluble chitosan-base aggregation-induced light-emitting fluorescent probe |
| WO2016173386A1 (en) * | 2015-04-29 | 2016-11-03 | 南方医科大学 | Application of penta-substituted tetrahydropyrimidines in preparation of temperature-sensitive fluorescent material |
| CN108752512A (en) * | 2018-04-25 | 2018-11-06 | 西北师范大学 | Temperature response type AIE fluorescent polymers nano-particle and its synthetic method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2016173386A1 (en) * | 2015-04-29 | 2016-11-03 | 南方医科大学 | Application of penta-substituted tetrahydropyrimidines in preparation of temperature-sensitive fluorescent material |
| CN104945537A (en) * | 2015-05-26 | 2015-09-30 | 浙江大学 | Preparation method of water-soluble chitosan-base aggregation-induced light-emitting fluorescent probe |
| CN108752512A (en) * | 2018-04-25 | 2018-11-06 | 西北师范大学 | Temperature response type AIE fluorescent polymers nano-particle and its synthetic method and application |
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