CN108373534B - Quantum dot-loaded conjugated microporous polymer and preparation method thereof, quantum dot membrane and liquid crystal display module - Google Patents

Quantum dot-loaded conjugated microporous polymer and preparation method thereof, quantum dot membrane and liquid crystal display module Download PDF

Info

Publication number
CN108373534B
CN108373534B CN201810062789.1A CN201810062789A CN108373534B CN 108373534 B CN108373534 B CN 108373534B CN 201810062789 A CN201810062789 A CN 201810062789A CN 108373534 B CN108373534 B CN 108373534B
Authority
CN
China
Prior art keywords
quantum dot
microporous polymer
conjugated microporous
loaded
cmp
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.)
Active
Application number
CN201810062789.1A
Other languages
Chinese (zh)
Other versions
CN108373534A (en
Inventor
李刚
徐雍捷
李培源
徐良霞
陈冲
孙书政
刘伟
唐海江
张彦
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ningbo Exciton Technology Co Ltd
Original Assignee
Ningbo Exciton Technology Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Ningbo Exciton Technology Co Ltd filed Critical Ningbo Exciton Technology Co Ltd
Priority to CN201810062789.1A priority Critical patent/CN108373534B/en
Publication of CN108373534A publication Critical patent/CN108373534A/en
Application granted granted Critical
Publication of CN108373534B publication Critical patent/CN108373534B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
    • C08G73/0644—Poly(1,3,5)triazines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/414—Additional features of adhesives in the form of films or foils characterized by the presence of essential components presence of a copolymer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00—Presence of (meth)acrylic polymer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2479/00—Presence of polyamine or polyimide

Abstract

The invention relates to the field of quantum dots and quantum dot films, in particular to a quantum dot-loaded conjugated microporous polymer and a preparation method thereof, a quantum dot film and a liquid crystal display module. In order to solve the problem that the existing quantum dots are easy to agglomerate, the invention provides a quantum dot-loaded conjugated microporous polymer and a preparation method thereof, a quantum dot membrane and a liquid crystal display module. The quantum dots are adsorbed on the surface of the conjugated microporous polymer. The quantum dot-loaded conjugated microporous polymer provided by the invention has good compatibility with an organic polymer glue system, overcomes the problem that quantum dots are easy to agglomerate, and reduces the using amount of the quantum dots; the quantum dot film provided by the invention has more excellent optical performance. The preparation method of the quantum dot-loaded conjugated microporous polymer provided by the invention is simple in process, strong in controllability and lower in cost, and can be used for rapidly realizing large-scale production and customized grade fine application.

Description

Quantum dot-loaded conjugated microporous polymer and preparation method thereof, quantum dot membrane and liquid crystal display module
Technical Field
The invention relates to the field of quantum dots and quantum dot films, in particular to a quantum dot-loaded conjugated microporous polymer and a preparation method thereof, a quantum dot film and a liquid crystal display module.
Background
Quantum Dots (QDs) are three-dimensional clusters of nanometer-scale dimensions and are therefore also referred to as nanodots. Wherein the II-VI type quantum dots composed of the elements of the second subgroup and the sixth main group have special and excellent fluorescence emission properties. The surface effect, quantum size and macroscopic tunnel effect of the material with the nanoscale semiconductor structure enable the material to show physical and chemical properties which are not possessed by a plurality of common materials, so that quantum dots are widely and deeply researched. Particularly, the quantum dot shows unique luminescence characteristics due to the fact that the diameter of the quantum dot is approximate to the exciton Bohr radius (10nm), so that the quantum dot has good application prospects in the aspects of luminescent materials, displays and the like.
However, at present, the following problems are often encountered in the use process of quantum dots: the first is that the dispersion is difficult and agglomeration is easy. The inorganic quantum dots are nanoparticles with small particle size, large specific surface area and high surface energy, so that agglomeration and depolymerization are easy to occur in the storage and application processes, and the inorganic quantum dots are difficult to disaggregate when being added into an organic glue system with high viscosity, so that the inorganic quantum dots are easy to disperse unevenly and agglomerate due to poor compatibility. The agglomeration of quantum dots can affect the transparency, light transmittance and luminous effect of the product. Secondly, the use and operation are inconvenient. At present, quantum dots are mainly stored in an organic solvent, so that the operation is complex when the quantum dots are applied to LED packaging, and the production cost and difficulty are increased when the solvent is removed. Thirdly, the quantum dots have poor oxidation resistance. The quantum dots are contacted with air in the using process and are easily oxidized by oxygen and water vapor in the air to cause the reduction of fluorescence intensity. Fourthly, the utilization rate of the blue light by the red and green quantum dots is relatively low, and the fluorescence quantum efficiency can not be effectively exerted.
The traditional quantum dot preparation and application scheme has inherent defects and limits the application of quantum dots in the display field, so that a novel quantum dot preparation technology needs to be researched to solve the problem of poor compatibility of inorganic quantum dots and an organic glue system.
Disclosure of Invention
In order to solve the problem that the existing quantum dots are easy to agglomerate, the invention provides a quantum dot-loaded conjugated microporous polymer and a preparation method thereof, a quantum dot membrane and a liquid crystal display module. The quantum dot-loaded conjugated microporous polymer provided by the invention has good compatibility with an organic polymer glue system, overcomes the problem that quantum dots are easy to agglomerate, and reduces the using amount of the quantum dots; the quantum dot film provided by the invention has more excellent optical performance. The preparation method of the quantum dot-loaded conjugated microporous polymer provided by the invention is simple in process, strong in controllability and lower in cost, and can be used for rapidly realizing large-scale production and customized grade fine application.
In order to solve the technical problems, the invention provides the following technical scheme:
the invention provides a quantum dot-loaded conjugated microporous polymer, wherein quantum dots are adsorbed on the surface of the conjugated microporous polymer.
Further, the structural formula of the repeating unit in the conjugated microporous polymer is as follows:
Figure BDA0001555823540000031
further, the quantum dots are selected from green quantum dots, red quantum dots or a mixture of the green quantum dots and the red quantum dots.
Further, the weight ratio of the quantum dots to the conjugated microporous polymer in the quantum dot-loaded conjugated microporous polymer is 1: 1.
further, the specific surface area of the conjugated microporous polymer is 267-843m2/g。
Further, the quantum dots are composed of green quantum dots and red quantum dots.
Further, the weight ratio of the green quantum dots to the red quantum dots is 1: 1.
further, the particle size of the green quantum dots is 3.1nm, and the particle size of the red quantum dots is 6.2 nm.
In the preparation process, the quantum dots are firstly prepared into a quantum dot dispersion liquid.
The quantum dot dispersion liquid is a cadmium selenide IBOA (isobornyl acrylate) solution with high water and oxygen resistance, and comprises a green quantum dot dispersion liquid and a red quantum dot dispersion liquid.
The green quantum dot dispersion comprises 15 wt% of green quantum dots, and the red quantum dot dispersion comprises 15 wt% of red quantum dots.
The present invention also provides a method for preparing a quantum dot-supported conjugated microporous polymer, the method comprising the steps of:
(1) preparation of Conjugated Microporous Polymer (CMP): 1, 4-dicyanobenzene and zinc chloride powder are uniformly mixed and put into a quartz tube, then the quartz tube is vacuumized, fused and sealed, and is placed into a tube furnace to be heated for 20-80 hours at the temperature of 200-; after cooling to room temperature, taking out the powder in the quartz tube, and obtaining the required conjugate microporous polymer CMP after filtering, washing and Soxhlet extraction;
(2) preparing a quantum dot-loaded conjugated microporous polymer: fully stirring and uniformly mixing the quantum dot dispersion liquid and the conjugated microporous polymer, then sealing the uniformly mixed slurry into a polytetrafluoroethylene hydrothermal reaction kettle, and placing the kettle in a high-temperature oven at 20-100 ℃ for 12 hours; and after cooling completely, carrying out suction filtration on the slurry, washing the slurry with deionized water, ethanol and chloroform, and carrying out vacuum drying at 60 ℃ to prepare the quantum dot-loaded conjugated microporous polymer (QD-CMP).
Further, in the step (1), the quartz tube is placed in a tube furnace and heated for 40 hours at 600 ℃ under a nitrogen atmosphere.
Further, the hydrothermal reaction kettle in the step (2) is placed in a high-temperature oven at 60 ℃.
Further, in the step (1), the molar ratio of the 1, 4-dinitrile benzene to the anhydrous zinc chloride powder is 1: 0.1-20.
Further, in the step (1), the molar ratio of the 1, 4-dinitrile benzene to the anhydrous zinc chloride powder is preferably 1: 2.
furthermore, the purity of the zinc chloride is 99.99%, and the water content in the powder is required to be lower than 0.1ppm so as to avoid the influence of water on the polymerization reaction.
Furthermore, the molar ratio of the 1, 4-dinitrile benzene to the zinc chloride can be adjusted according to the requirement of the specific surface area of the required conjugated microporous polymer.
Further, the charge ratio of the quantum dot dispersion liquid and the conjugated microporous polymer in the step (2) is 6.6: 1.
further, the quantum dot dispersion liquid in the step (2) includes a red quantum dot dispersion liquid and a green quantum dot dispersion liquid, and the feeding ratio of the red quantum dot dispersion liquid to the green quantum dot dispersion liquid to the conjugated microporous polymer is 3.3: 3.3: 1.
the feeding ratio is the weight ratio of the feeding.
The mass ratio of the red quantum dot dispersion liquid to the green quantum dot dispersion liquid can be adjusted according to the specific optical display performance requirement.
Further, the yield of the conjugated microporous polymer prepared in the step (1) is 77-99%.
Further, the loading rate of the quantum dot-loaded conjugated microporous polymer prepared in the step (2) is 75-98%.
The quantum dot-loaded conjugated microporous polymer provided by the invention can be applied to quantum dot diaphragms and liquid crystal display modules.
The invention also provides a quantum dot diaphragm which comprises a quantum dot glue layer, wherein the quantum dot glue layer comprises the conjugated microporous polymer loaded with quantum dots.
The quantum dot film is also called quantum dot film.
The invention also provides a preparation method of the quantum dot diaphragm, which comprises the following steps: uniformly stirring the quantum dot-loaded conjugated microporous polymer and the acrylate UV curing adhesive to form a coating liquid, uniformly coating the coating liquid on the inner surfaces of the two barrier films, bonding the barrier films, curing the coating liquid through a UV lamp to form a quantum dot adhesive layer, and preparing the quantum dot membrane.
Further, the method comprises the following steps:
(1) weighing 40g of quantum dot-loaded conjugated microporous polymer (RQD-CMP) and 100g of isobornyl acrylate (IBOA) and uniformly stirring on a vibrator, adding the mixture into 1000g of mixed solution of acrylate UV curing glue, mechanically stirring for 2 hours, and standing to obtain mixed fluorescent glue;
(2) and (3) injecting the uniformly mixed fluorescent glue into a die head through a screw pump, uniformly coating the glue between two PET films, and performing rolling, ultraviolet irradiation curing and cutting to obtain a quantum dot film sheet with the size of A4, wherein the thickness of the quantum dot glue layer is 100 microns.
The invention also provides a liquid crystal display module which comprises the quantum dot film, wherein the quantum dot film comprises a quantum dot glue layer, and the quantum dot glue layer comprises a quantum dot-loaded conjugated microporous polymer.
Furthermore, the liquid crystal display module sequentially comprises a light source, a light guide plate, a quantum dot membrane, a prism sheet, a polarizer and a liquid crystal panel.
Further, the light source is a direct-in type or side-in type light source. The liquid crystal display module is of a direct-in type or a side-in type.
Compared with the prior art, the invention has the beneficial effects that:
the quantum dot loaded conjugated microporous polymer provided by the invention loads red and green quantum dots on the conjugated microporous polymer, so that the introduction of a single white dot is realized on a smaller scale, and the uniformity of the color coordinate of display equipment is greatly improved; the invention fully utilizes the optical advantages of the conjugated microporous polymer, reduces the actual usage amount of the quantum dots, reduces the cost and simultaneously improves the overall optical performance of the quantum dot film; the inorganic quantum dots are loaded on the organic conjugated microporous polymer with large specific surface area, so that the defect of poor compatibility of the conventional inorganic quantum dots and organic polymer glue systems is fundamentally overcome, and unstable factors such as uneven dispersion, difficulty in controlling the thickness of a membrane, large color coordinate offset and the like in the production process caused by system incompatibility can be avoided; the preparation process of the quantum dot loaded conjugated microporous polymer and the quantum dot membrane provided by the invention is simple, and the raw materials are cheap and easy to obtain, so that the quantum dot loaded conjugated microporous polymer and the quantum dot membrane have wide application capability and feasibility of mass production.
Drawings
FIG. 1 is a schematic chemical structure diagram of a Conjugated Microporous Polymer (CMP) provided by the present invention;
FIG. 2 is a scanning electron micrograph of a Conjugated Microporous Polymer (CMP) prepared in example 2 of the present invention;
FIG. 3 is an X-ray diffraction pattern of a Conjugated Microporous Polymer (CMP) prepared in example 2 of the present invention;
FIG. 4 is a Fourier infrared spectrum of a Conjugated Microporous Polymer (CMP) prepared in example 2 of the present invention;
FIG. 5 is a fluorescence emission spectrum of a conjugated microporous polymer (QD-CMP) loaded with red and green quantum dots prepared in example 2 of the present invention;
fig. 6 is a fluorescence emission spectrum of the green quantum dot-loaded conjugated microporous polymer (GQD-CMP) prepared in example 11 of the present invention;
FIG. 7 is a fluorescence emission spectrum of a red quantum dot-loaded conjugated microporous polymer (RQD-CMP) prepared in example 12 of the present invention;
fig. 8 is a schematic structural diagram of a direct-type liquid crystal display module according to the present invention.
Detailed Description
The following will clearly and completely describe the technical solutions in the embodiments of the present invention, and it is obvious that the described embodiment is only one embodiment of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The preparation method of the quantum dot-loaded conjugated microporous polymer provided by the invention comprises the following steps:
(1) preparation of Conjugated Microporous Polymer (CMP): 1, 4-dicyanobenzene and zinc chloride powder are uniformly mixed and put into a quartz tube, then the quartz tube is vacuumized, fused and sealed, and is placed into a tube furnace to be heated for 20-80 hours at the temperature of 200-1200 ℃ under the nitrogen atmosphere. After cooling to room temperature, taking out the powder in the quartz tube, and obtaining the required conjugate microporous polymer CMP after filtering, washing and Soxhlet extraction;
(2) preparing a quantum dot-loaded conjugated microporous polymer: and fully stirring and uniformly mixing the quantum dot dispersion liquid and the conjugated microporous polymer, then sealing the uniformly mixed slurry into a polytetrafluoroethylene hydrothermal reaction kettle, and placing the kettle in a high-temperature oven at 40-100 ℃ for 12 hours. And after cooling completely, carrying out suction filtration on the slurry, washing the slurry with deionized water, ethanol and chloroform, and carrying out vacuum drying at 60 ℃ to prepare the quantum dot-loaded conjugated microporous polymer (QD-CMP).
The preparation method of the quantum dot diaphragm provided by the invention comprises the following steps:
(1) weighing 40g of quantum dot-loaded conjugated microporous polymer (RQD-CMP) and 100g of isobornyl acrylate (IBOA) and uniformly stirring on a vibrator, adding the mixture into 1000g of mixed solution of acrylate UV curing glue, mechanically stirring for 2 hours, and standing to obtain mixed fluorescent glue;
(2) and (3) injecting the uniformly mixed fluorescent glue into a die head through a screw pump, uniformly coating the glue between two PET films, and performing rolling, ultraviolet irradiation curing and cutting to obtain a quantum dot film sheet with the size of A4, wherein the thickness of the quantum dot glue layer is 100 microns.
The conjugated microporous polymers provided in the examples of the present invention and comparative examples and quantum dot-loaded conjugated microporous polymers were tested for their relevant performance properties in the following manner.
1. Yield of conjugated microporous polymer: yield is the mass of the obtained conjugated microporous polymer after the reaction/the mass of the monomer added before the reaction;
2. loading ratio of the quantum dot-loaded conjugated microporous polymer: the loading rate is the mass of the quantum dot-loaded conjugated microporous polymer/(the mass of the quantum dot + the loaded conjugated microporous polymer);
3. dispersibility of quantum dot-supporting conjugated microporous polymer: 10g of the prepared quantum dot-loaded conjugated microporous polymer was added to 100ml of IBOA solution and mechanically stirred for 15min, and then the mixture was allowed to stand and observed for sedimentation. The criteria are as follows: the method is good: no significant sedimentation was observed after 5 hours of standing; in general: no obvious sedimentation is observed after standing for 1 hour, and partial sedimentation is observed after standing for 5 hours; poor results are obtained: significant settling was observed within 1 hour of standing. Poor dispersion indicates failure.
4. Specific surface area of the conjugated microporous polymer: 100mg of the sample is loaded into a nitrogen adsorption instrument, the nitrogen adsorption condition of the sample is tested in the liquid nitrogen atmosphere, and the nitrogen adsorption condition is automatically converted into the specific surface area.
The main optical properties of the quantum dot films provided by the present invention were tested in the following manner.
1. Light transmittance and haze test: a quantum dot film to be tested of A4 is taken and put into a light transmittance haze tester (NDH7000) to be tested to test the light transmittance or haze value.
2. And (3) testing the brightness: the quantum dot film to be tested with the size of A4 is placed into a 10-inch backlight module according to a test framework (lateral backlight + the quantum dot film of the invention), and is lightened under the voltage of 24V, and the luminance of the quantum dot film is tested by a luminance instrument (CS-2000).
3. The optical evaluation criteria are as follows:
the method is good: the light transmittance of the film surface is more than 90 percent (inclusive), and the luminance is more than 3500 (inclusive);
preferably: the light transmittance of the film surface is more than 90 percent (contained), and the luminance is more than 3300 (contained);
in general: the light transmittance of the film surface is more than 90 percent (inclusive), and the luminance is more than 3100 (inclusive);
very poor: the light transmittance of the film surface is above 90% (inclusive), and the luminance is below 3000 (inclusive).
Example 1
Preparation of mono-Conjugated Microporous Polymer (CMP)
1, 4-dicyanobenzene (128g,1mol) and zinc chloride powder (13.6g,0.1mol) are uniformly mixed and filled into a quartz tube, and then the quartz tube is vacuumized, fused and sealed, and placed into a tube furnace to be heated for 40 hours at 600 ℃ under the nitrogen atmosphere. And after cooling to room temperature, taking out the powder in the quartz tube, and performing suction filtration, washing and Soxhlet extraction to obtain the required conjugate microporous polymer CMP with the yield of 94%.
Preparation of quantum dot-loaded conjugated microporous polymer (QD-CMP)
42.6g of 15 wt% green cadmium selenide quantum dot dispersion liquid (the dosage of the green cadmium selenide is 6.4g), 42.6g of 15 wt% red cadmium selenide quantum dot dispersion liquid (the dosage of the red cadmium selenide is 6.4g) and 12.8g of the conjugated microporous polymer CMP are fully stirred and uniformly mixed, and then the uniformly mixed slurry is sealed in a polytetrafluoroethylene hydrothermal reaction kettle and is placed in a high-temperature oven at 60 ℃ for 12 hours. After cooling completely, the slurry is filtered, washed by 100ml of deionized water, ethanol and chloroform respectively, and dried in vacuum at 60 ℃ for 24 hours to prepare the quantum dot-loaded conjugated microporous polymer (QD-CMP), wherein the loading rate is 93%.
The results of the performance tests on the prepared conjugated microporous polymer and the quantum dot-loaded conjugated microporous polymer are shown in table 1.
Example 2
The conjugated microporous polymer and the quantum dot-loaded conjugated microporous polymer as provided in example 1 were prepared by uniformly mixing 1, 4-dinitrile benzene (128g,1mol), zinc chloride powder (272g,2mol) and charging into a quartz tube (CMP).
The results of the performance tests on the prepared conjugated microporous polymer and the quantum dot-loaded conjugated microporous polymer are shown in table 1.
Example 3
Preparation of mono-Conjugated Microporous Polymer (CMP)
The conjugated microporous polymer and quantum dot-loaded conjugated microporous polymer provided in example 1 were prepared by uniformly mixing 1, 4-dinitrile benzene (128g,1mol), zinc chloride powder (2720g,20mol) and charging into a quartz tube (CMP).
The results of the performance tests on the prepared conjugated microporous polymer and the quantum dot-loaded conjugated microporous polymer are shown in table 1.
Example 4
Preparation of mono-Conjugated Microporous Polymer (CMP)
1, 4-dicyanobenzene (128g,1mol) and zinc chloride powder (272g,2mol) are uniformly mixed and put into a quartz tube, and then the quartz tube is vacuumized, fused and sealed, and is placed in a tube furnace to be heated for 40 hours at 200 ℃ under the nitrogen atmosphere. And after cooling to room temperature, taking out the powder in the quartz tube, and performing suction filtration, washing and Soxhlet extraction to obtain the required conjugate microporous polymer CMP with the yield of 85%.
Preparation of quantum dot-loaded conjugated microporous polymer (QD-CMP)
42.6g of 15 wt% green cadmium selenide quantum dot dispersion liquid (the dosage of the green cadmium selenide is 6.4g), 42.6g of 15 wt% red cadmium selenide quantum dot dispersion liquid (the dosage of the red cadmium selenide is 6.4g) and 12.8g of the conjugated microporous polymer CMP are fully stirred and uniformly mixed, and then the uniformly mixed slurry is sealed in a polytetrafluoroethylene hydrothermal reaction kettle and is placed in a high-temperature oven at 60 ℃ for 12 hours. And after cooling completely, filtering the slurry, washing the slurry by using 100ml of deionized water, ethanol and chloroform respectively, and drying the slurry in vacuum at 60 ℃ for 24 hours to prepare the quantum dot-loaded conjugated microporous polymer (QD-CMP) with the loading rate of 78%.
The results of the performance tests on the prepared conjugated microporous polymer and the quantum dot-loaded conjugated microporous polymer are shown in table 1.
Example 5
Preparation of mono-Conjugated Microporous Polymer (CMP)
1, 4-dicyanobenzene (128g,1mol) and zinc chloride powder (272g,2mol) are uniformly mixed and put into a quartz tube, and then the quartz tube is vacuumized, fused and sealed, and is placed in a tube furnace to be heated for 40 hours at 1200 ℃ under the nitrogen atmosphere. And after cooling to room temperature, taking out the powder in the quartz tube, and performing suction filtration, washing and Soxhlet extraction to obtain the required conjugate microporous polymer CMP with the yield of 83%.
Preparation of quantum dot-loaded conjugated microporous polymer (QD-CMP)
42.6g of 15 wt% green cadmium selenide quantum dot dispersion liquid (the dosage of the green cadmium selenide is 6.4g), 42.6g of 15 wt% red cadmium selenide quantum dot dispersion liquid (the dosage of the red cadmium selenide is 6.4g) and 12.8g of the conjugated microporous polymer CMP are fully stirred and uniformly mixed, and then the uniformly mixed slurry is sealed in a polytetrafluoroethylene hydrothermal reaction kettle and is placed in a high-temperature oven at 60 ℃ for 12 hours. And after cooling completely, filtering the slurry, washing the slurry by using 100ml of deionized water, ethanol and chloroform respectively, and drying the slurry in vacuum at 60 ℃ for 24 hours to prepare the quantum dot-loaded conjugated microporous polymer (QD-CMP), wherein the loading rate is 76%.
The results of the performance tests on the prepared conjugated microporous polymer and the quantum dot-loaded conjugated microporous polymer are shown in table 1.
Example 6
Preparation of mono-Conjugated Microporous Polymer (CMP)
1, 4-dicyanobenzene (128g,1mol) and zinc chloride powder (272g,2mol) are uniformly mixed and put into a quartz tube, and then the quartz tube is vacuumized, fused and sealed, and is placed in a tube furnace to be heated for 20 hours at 600 ℃ under the nitrogen atmosphere. After cooling to room temperature, taking out the powder in the quartz tube, and obtaining the required conjugate microporous polymer CMP after suction filtration, washing and Soxhlet extraction, wherein the yield is 77%.
Preparation of quantum dot-loaded conjugated microporous polymer (QD-CMP)
42.6g of 15 wt% green cadmium selenide quantum dot dispersion liquid (the dosage of the green cadmium selenide is 6.4g), 42.6g of 15 wt% red cadmium selenide quantum dot dispersion liquid (the dosage of the red cadmium selenide is 6.4g) and 12.8g of the conjugated microporous polymer CMP are fully stirred and uniformly mixed, and then the uniformly mixed slurry is sealed in a polytetrafluoroethylene hydrothermal reaction kettle and is placed in a high-temperature oven at 60 ℃ for 12 hours. And after cooling completely, filtering the slurry, washing the slurry by using 100ml of deionized water, ethanol and chloroform respectively, and drying the slurry in vacuum at 60 ℃ for 24 hours to prepare the quantum dot-loaded conjugated microporous polymer (QD-CMP), wherein the loading rate is 83%.
The results of the performance tests on the prepared conjugated microporous polymer and the quantum dot-loaded conjugated microporous polymer are shown in table 1.
Example 7
Preparation of mono-Conjugated Microporous Polymer (CMP)
1, 4-dicyanobenzene (128g,1mol) and zinc chloride powder (272g,2mol) are uniformly mixed and put into a quartz tube, and then the quartz tube is vacuumized, fused and sealed, and is placed in a tube furnace to be heated for 80 hours at 600 ℃ under the nitrogen atmosphere. And after cooling to room temperature, taking out the powder in the quartz tube, and performing suction filtration, washing and Soxhlet extraction to obtain the required conjugate microporous polymer CMP with the yield of 81%.
Preparation of quantum dot-loaded conjugated microporous polymer (QD-CMP)
42.6g of 15 wt% green cadmium selenide quantum dot dispersion liquid (the dosage of the green cadmium selenide is 6.4g), 42.6g of 15 wt% red cadmium selenide quantum dot dispersion liquid (the dosage of the red cadmium selenide is 6.4g) and 12.8g of the conjugated microporous polymer CMP are fully stirred and uniformly mixed, and then the uniformly mixed slurry is sealed in a polytetrafluoroethylene hydrothermal reaction kettle and is placed in a high-temperature oven at 60 ℃ for 12 hours. And after cooling completely, filtering the slurry, washing the slurry by using 100ml of deionized water, ethanol and chloroform respectively, and drying the slurry in vacuum at 60 ℃ for 24 hours to prepare the quantum dot-loaded conjugated microporous polymer (QD-CMP) with the loading rate of 75%.
The results of the performance tests on the prepared conjugated microporous polymer and the quantum dot-loaded conjugated microporous polymer are shown in table 1.
Example 8
Preparation of mono-Conjugated Microporous Polymer (CMP)
1, 4-dicyanobenzene (128g,1mol) and zinc chloride powder (272g,2mol) are uniformly mixed and put into a quartz tube, and then the quartz tube is vacuumized, fused and sealed, and is placed in a tube furnace to be heated for 40 hours at 600 ℃ under the nitrogen atmosphere. And after cooling to room temperature, taking out the powder in the quartz tube, and performing suction filtration, washing and Soxhlet extraction to obtain the required conjugate microporous polymer CMP with the yield of 99%.
Preparation of quantum dot-loaded conjugated microporous polymer (QD-CMP)
42.6g of 15 wt% green cadmium selenide quantum dot dispersion liquid (the dosage of the green cadmium selenide is 6.4g), 42.6g of 15 wt% red cadmium selenide quantum dot dispersion liquid (the dosage of the red cadmium selenide is 6.4g) and 12.8g of the conjugated microporous polymer CMP are fully stirred and uniformly mixed, and then the uniformly mixed slurry is sealed in a polytetrafluoroethylene hydrothermal reaction kettle and is placed in a high-temperature oven at 40 ℃ for 12 hours. And after cooling completely, filtering the slurry, washing the slurry by using 100ml of deionized water, ethanol and chloroform respectively, and drying the slurry in vacuum at 60 ℃ for 24 hours to prepare the quantum dot-loaded conjugated microporous polymer (QD-CMP) with the loading rate of 76%.
The results of the performance tests on the prepared conjugated microporous polymer and the quantum dot-loaded conjugated microporous polymer are shown in table 1.
Example 9
Preparation of mono-Conjugated Microporous Polymer (CMP)
1, 4-dicyanobenzene (128g,1mol) and zinc chloride powder (272g,2mol) are uniformly mixed and put into a quartz tube, and then the quartz tube is vacuumized, fused and sealed, and is placed in a tube furnace to be heated for 40 hours at 600 ℃ under the nitrogen atmosphere. And after cooling to room temperature, taking out the powder in the quartz tube, and performing suction filtration, washing and Soxhlet extraction to obtain the required conjugate microporous polymer CMP with the yield of 99%.
Preparation of quantum dot-loaded conjugated microporous polymer (QD-CMP)
42.6g of 15 wt% green cadmium selenide quantum dot dispersion liquid (the dosage of the green cadmium selenide is 6.4g), 42.6g of 15 wt% red cadmium selenide quantum dot dispersion liquid (the dosage of the red cadmium selenide is 6.4g) and 12.8g of the conjugated microporous polymer CMP are fully stirred and uniformly mixed, and then the uniformly mixed slurry is sealed in a polytetrafluoroethylene hydrothermal reaction kettle and is placed in a high-temperature oven at 100 ℃ for 12 hours. And after cooling completely, filtering the slurry, washing the slurry by using 100ml of deionized water, ethanol and chloroform respectively, and drying the slurry in vacuum at 60 ℃ for 24 hours to prepare the quantum dot-loaded conjugated microporous polymer (QD-CMP) with the loading rate of 80%.
The results of the performance tests on the prepared conjugated microporous polymer and the quantum dot-loaded conjugated microporous polymer are shown in table 1.
Example 10
40g of the quantum dot-loaded conjugated microporous polymer (QD-CMP) prepared in example 2 and 100g of isobornyl acrylate (IBOA) were weighed, stirred and mixed uniformly on a vibrator, added into a mixed solution of 1000g of acrylate UV curing glue, mechanically stirred for 2 hours, and kept stand to obtain mixed fluorescent glue.
And (3) injecting the uniformly mixed fluorescent glue into a die head through a screw pump, uniformly coating the glue between two PET films, and performing rolling, ultraviolet irradiation curing and cutting to obtain a quantum dot film sheet with the size of A4, wherein the thickness of the quantum dot glue layer is 100 microns.
The performance test results of the prepared quantum dot film sheet are shown in table 2.
Example 11
Preparation of mono-Conjugated Microporous Polymer (CMP)
1, 4-dicyanobenzene (128g,1mol) and zinc chloride powder (272g,2mol) are uniformly mixed and put into a quartz tube, and then the quartz tube is vacuumized, fused and sealed, and is placed in a tube furnace to be heated for 40 hours at 600 ℃ under the nitrogen atmosphere. And after cooling to room temperature, taking out the powder in the quartz tube, and performing suction filtration, washing and Soxhlet extraction to obtain the required conjugate microporous polymer CMP with the yield of 99%.
Preparation of quantum dot-loaded conjugated microporous polymer (GQD-CMP)
85.2g of 15 wt% green cadmium selenide quantum dot dispersion (the dosage of the green cadmium selenide is 12.8g) and 12.8g of the conjugated microporous polymer CMP are fully stirred and uniformly mixed, and then the uniformly mixed slurry is sealed into a polytetrafluoroethylene hydrothermal reaction kettle and placed in a high-temperature oven at 20 ℃ for 12 hours. And after cooling completely, filtering the slurry, washing the slurry by using 100ml of deionized water, ethanol and chloroform respectively, and drying the slurry in vacuum at 60 ℃ for 24 hours to prepare the quantum dot-loaded conjugated microporous polymer (GQD-CMP), wherein the loading rate is 96%.
The results of the performance tests on the prepared conjugated microporous polymer and the quantum dot-loaded conjugated microporous polymer are shown in table 1.
Example 12
Preparation of mono-Conjugated Microporous Polymer (CMP)
1, 4-dicyanobenzene (128g,1mol) and zinc chloride powder (272g,2mol) are uniformly mixed and put into a quartz tube, and then the quartz tube is vacuumized, fused and sealed, and is placed in a tube furnace to be heated for 40 hours at 600 ℃ under the nitrogen atmosphere. And after cooling to room temperature, taking out the powder in the quartz tube, and performing suction filtration, washing and Soxhlet extraction to obtain the required conjugate microporous polymer CMP with the yield of 99%.
Secondly, preparation of quantum dot-loaded conjugated microporous polymer (RQD-CMP)
85.2g of 15 wt% red cadmium selenide quantum dot dispersion (the dosage of red cadmium selenide is 12.8g) and 12.8g of the conjugated microporous polymer CMP are fully stirred and uniformly mixed, and then the uniformly mixed slurry is sealed into a polytetrafluoroethylene hydrothermal reaction kettle and placed in a high-temperature oven at 20 ℃ for 12 hours. After cooling completely, the slurry is filtered, washed by 100ml of deionized water, ethanol and chloroform respectively, and dried in vacuum at 60 ℃ for 24 hours to prepare the quantum dot-loaded conjugated microporous polymer (RQD-CMP) with the loading rate of 94%.
The results of the performance tests on the prepared conjugated microporous polymer and the quantum dot-loaded conjugated microporous polymer are shown in table 1.
Example 13
40g of the quantum dot-loaded conjugated microporous polymer (GQD-CMP) prepared in example 11 and 100g of isobornyl acrylate (IBOA) were weighed out and mixed uniformly on a shaker, added to a mixed solution of 1000g of acrylate UV curing glue and mechanically stirred for 2 hours, and then left to stand to obtain the mixed fluorescent glue.
And (3) injecting the uniformly mixed fluorescent glue into a die head through a screw pump, uniformly coating the glue between two PET films, and performing rolling, ultraviolet irradiation curing and cutting to obtain a quantum dot film sheet with the size of A4, wherein the thickness of the quantum dot glue layer is 100 microns.
The performance test results of the prepared quantum dot film sheet are shown in table 2.
Example 14
40g of the quantum dot-loaded conjugated microporous polymer (RQD-CMP) prepared in example 12 and 100g of isobornyl acrylate (IBOA) were weighed out and mixed uniformly on a shaker, added to a mixed solution of 1000g of acrylate UV curing glue and mechanically stirred for 2 hours, and then left to stand to obtain the mixed fluorescent glue.
And (3) injecting the uniformly mixed fluorescent glue into a die head through a screw pump, uniformly coating the glue between two PET films, and performing rolling, ultraviolet irradiation curing and cutting to obtain a quantum dot film sheet with the size of A4, wherein the thickness of the quantum dot glue layer is 100 microns.
The performance test results of the prepared quantum dot film sheet are shown in table 2.
Comparative example 1
Preparation of mono-Conjugated Microporous Polymer (CMP)
1, 4-dicyanobenzene (128g,1mol) and zinc chloride powder (6800g,50mol) are uniformly mixed and filled into a quartz tube, and then the quartz tube is vacuumized, fused and sealed, and placed into a tube furnace to be heated for 40 hours at 600 ℃ under the nitrogen atmosphere. And after cooling to room temperature, taking out the powder in the quartz tube, and performing suction filtration, washing and Soxhlet extraction to obtain the required conjugate microporous polymer CMP with the yield of 20%.
Preparation of quantum dot-loaded conjugated microporous polymer (QD-CMP)
4.26g of 15 wt% green cadmium selenide quantum dot dispersion liquid (the dosage of the green cadmium selenide is 6.4g), 42.6g of 15 wt% red cadmium selenide quantum dot dispersion liquid (the dosage of the red cadmium selenide is 6.4g) and 12.8g of the conjugated microporous polymer CMP are fully stirred and uniformly mixed, and then the uniformly mixed slurry is sealed in a polytetrafluoroethylene hydrothermal reaction kettle and is placed in a high-temperature oven at 60 ℃ for 12 hours. And after cooling completely, filtering the slurry, washing the slurry by using 100ml of deionized water, ethanol and chloroform respectively, and drying the slurry in vacuum at 60 ℃ for 24 hours to prepare the quantum dot-loaded conjugated microporous polymer (QD-CMP), wherein the loading rate is 13%.
The results of the performance tests on the prepared conjugated microporous polymer and the quantum dot-loaded conjugated microporous polymer are shown in table 1.
Comparative example 2
Preparation of mono-Conjugated Microporous Polymer (CMP)
1, 4-dicyanobenzene (128g,1mol) and zinc chloride powder (1.36g,0.01mol) are mixed uniformly and filled into a quartz tube, and then the quartz tube is vacuumized, fused and sealed, and placed into a tube furnace to be heated for 40 hours at 600 ℃ under the nitrogen atmosphere. And after cooling to room temperature, taking out the powder in the quartz tube, and performing suction filtration, washing and Soxhlet extraction to obtain the required conjugate microporous polymer CMP with the yield of 12%.
Preparation of quantum dot-loaded conjugated microporous polymer (QD-CMP)
42.6g of 15 wt% green cadmium selenide quantum dot dispersion liquid (the dosage of the green cadmium selenide is 6.4g), 42.6g of 15 wt% red cadmium selenide quantum dot dispersion liquid (the dosage of the red cadmium selenide is 6.4g) and 12.8g of the conjugated microporous polymer CMP are fully stirred and uniformly mixed, and then the uniformly mixed slurry is sealed in a polytetrafluoroethylene hydrothermal reaction kettle and is placed in a high-temperature oven at 60 ℃ for 12 hours. And after cooling completely, filtering the slurry, washing the slurry by using 100ml of deionized water, ethanol and chloroform respectively, and drying the slurry in vacuum at 60 ℃ for 24 hours to prepare the quantum dot-loaded conjugated microporous polymer (QD-CMP), wherein the loading rate is 23%.
The results of the performance tests on the prepared conjugated microporous polymer and the quantum dot-loaded conjugated microporous polymer are shown in table 1.
Comparative example 3
Preparation of mono-Conjugated Microporous Polymer (CMP)
1, 4-dicyanobenzene (128g,1mol) and zinc chloride powder (272g,2mol) are uniformly mixed and put into a quartz tube, and then the quartz tube is vacuumized, fused and sealed, and is placed in a tube furnace to be heated for 40 hours at 50 ℃ under the nitrogen atmosphere. And after cooling to room temperature, taking out the powder in the quartz tube, and performing suction filtration, washing and Soxhlet extraction to obtain the required conjugate microporous polymer CMP with the yield of 12%.
Preparation of quantum dot-loaded conjugated microporous polymer (QD-CMP)
42.6g of 15 wt% green cadmium selenide quantum dot dispersion liquid (the dosage of the green cadmium selenide is 6.4g), 42.6g of 15 wt% red cadmium selenide quantum dot dispersion liquid (the dosage of the red cadmium selenide is 6.4g) and 12.8g of the conjugated microporous polymer CMP are fully stirred and uniformly mixed, and then the uniformly mixed slurry is sealed in a polytetrafluoroethylene hydrothermal reaction kettle and is placed in a high-temperature oven at 60 ℃ for 12 hours. And after cooling completely, filtering the slurry, washing the slurry by using 100ml of deionized water, ethanol and chloroform respectively, and drying the slurry in vacuum at 60 ℃ for 24 hours to prepare the quantum dot-loaded conjugated microporous polymer (QD-CMP), wherein the loading rate is 23%.
The results of the performance tests on the prepared conjugated microporous polymer and the quantum dot-loaded conjugated microporous polymer are shown in table 1.
Comparative example 4
Preparation of mono-Conjugated Microporous Polymer (CMP)
1, 4-dicyanobenzene (128g,1mol) and zinc chloride powder (272g,2mol) are uniformly mixed and put into a quartz tube, and then the quartz tube is vacuumized, fused and sealed, and is placed in a tube furnace to be heated for 10 hours at 600 ℃ under the nitrogen atmosphere. And after cooling to room temperature, taking out the powder in the quartz tube, and performing suction filtration, washing and Soxhlet extraction to obtain the required conjugate microporous polymer CMP with the yield of 32%.
Preparation of quantum dot-loaded conjugated microporous polymer (QD-CMP)
42.6g of 15 wt% green cadmium selenide quantum dot dispersion liquid (the dosage of the green cadmium selenide is 6.4g), 42.6g of 15 wt% red cadmium selenide quantum dot dispersion liquid (the dosage of the red cadmium selenide is 6.4g) and 12.8g of the conjugated microporous polymer CMP are fully stirred and uniformly mixed, and then the uniformly mixed slurry is sealed in a polytetrafluoroethylene hydrothermal reaction kettle and is placed in a high-temperature oven at 60 ℃ for 12 hours. And after cooling completely, filtering the slurry, washing the slurry by using 100ml of deionized water, ethanol and chloroform respectively, and drying the slurry in vacuum at 60 ℃ for 24 hours to prepare the quantum dot-loaded conjugated microporous polymer (QD-CMP), wherein the loading rate is 43%.
The results of the performance tests on the prepared conjugated microporous polymer and the quantum dot-loaded conjugated microporous polymer are shown in table 1.
Comparative example 5
Preparation of mono-Conjugated Microporous Polymer (CMP)
1, 4-dicyanobenzene (128g,1mol) and zinc chloride powder (272g,2mol) are uniformly mixed and put into a quartz tube, and then the quartz tube is vacuumized, fused and sealed, and is placed in a tube furnace to be heated for 40 hours at 600 ℃ under the nitrogen atmosphere. And after cooling to room temperature, taking out the powder in the quartz tube, and performing suction filtration, washing and Soxhlet extraction to obtain the required conjugate microporous polymer CMP with the yield of 99%.
Preparation of quantum dot-loaded conjugated microporous polymer (QD-CMP)
42.6g of 15 wt% green cadmium selenide quantum dot dispersion liquid (the dosage of the green cadmium selenide is 6.4g), 42.6g of 15 wt% red cadmium selenide quantum dot dispersion liquid (the dosage of the red cadmium selenide is 6.4g) and 12.8g of the conjugated microporous polymer CMP are fully stirred and uniformly mixed, and then the uniformly mixed slurry is sealed in a polytetrafluoroethylene hydrothermal reaction kettle and is placed in a high-temperature oven at 20 ℃ for 12 hours. And after cooling completely, filtering the slurry, washing the slurry by using 100ml of deionized water, ethanol and chloroform respectively, and drying the slurry in vacuum at 60 ℃ for 24 hours to prepare the quantum dot-loaded conjugated microporous polymer (QD-CMP), wherein the loading rate is 27%.
The results of the performance tests on the prepared conjugated microporous polymer and the quantum dot-loaded conjugated microporous polymer are shown in table 1.
Comparative example 6
Preparation of mono-Conjugated Microporous Polymer (CMP)
1, 4-dicyanobenzene (128g,1mol) and zinc chloride powder (272g,2mol) are uniformly mixed and put into a quartz tube, and then the quartz tube is vacuumized, fused and sealed, and is placed in a tube furnace to be heated for 40 hours at 600 ℃ under the nitrogen atmosphere. And after cooling to room temperature, taking out the powder in the quartz tube, and performing suction filtration, washing and Soxhlet extraction to obtain the required conjugate microporous polymer CMP with the yield of 99%.
Preparation of quantum dot-loaded conjugated microporous polymer (QD-CMP)
42.6g of 15 wt% green cadmium selenide quantum dot dispersion liquid (the dosage of the green cadmium selenide is 6.4g), 42.6g of 15 wt% red cadmium selenide quantum dot dispersion liquid (the dosage of the red cadmium selenide is 6.4g) and 12.8g of the conjugated microporous polymer CMP are fully stirred and uniformly mixed, and then the uniformly mixed slurry is sealed in a polytetrafluoroethylene hydrothermal reaction kettle and is placed in a high-temperature oven at 150 ℃ for 24 hours. And after cooling completely, filtering the slurry, washing the slurry by using 100ml of deionized water, ethanol and chloroform respectively, and drying the slurry in vacuum at 60 ℃ for 24 hours to prepare the quantum dot-loaded conjugated microporous polymer (QD-CMP), wherein the loading rate is 38%.
The results of the performance tests on the prepared conjugated microporous polymer and the quantum dot-loaded conjugated microporous polymer are shown in table 1.
Table 1 results of performance testing of the conjugated microporous polymers and composites provided in examples 1-9, 11-12 and comparative examples 1-6
Yield% Load ratio% Specific surface area (m)2/g) Dispersibility
Example 1 94 93 367 In general
Example 2 99 98 843 Is very good
Example 3 92 94 421 In general
Example 4 85 78 523 In general
Example 5 83 76 358 In general
Example 6 77 83 267 In general
Example 7 81 75 623 In general
Example 8 99 76 811 In general
Example 9 99 80 803 In general
Example 11 99 96 788 Is very good
Example 12 99 94 809 Is very good
Comparative example 1 20 13 45 Not good at
Comparative example 2 12 23 27 Not good at
Comparative example 3 12 23 12 Not good at
Comparative example 4 32 43 36 Not good at
Comparative example 5 99 27 767 Not good at
Comparative example 6 99 38 783 Not good at
Table 2 results of performance testing of quantum dot membranes provided in example 10 and examples 13-14
Light transmittance% Haze%) Luminance (cd/m)2) Optical Properties
Example 10 93.33 87.76 3657 Is very good
Example 13 91.58 88.63 3322 Is preferably used
Example 14 92.07 87.91 3392 Is preferably used
Fig. 2 is a Scanning Electron Micrograph (SEM) of the Conjugated Microporous Polymer (CMP) prepared in example 2, and the test results show that the resulting material is coarse porous particles.
Fig. 3 is an X-ray diffraction pattern (XRD) of the Conjugated Microporous Polymer (CMP) prepared in example 2, and the result shows that the resulting material has a significant carbon inclusion peak at an angle of 2 θ of about 25 °, indicating that the resulting Conjugated Microporous Polymer (CMP) is an amorphous polymer material stacked with conjugated planar structures.
FIG. 4 is a Fourier transform infrared (FT-IR) spectrum of the Conjugated Microporous Polymer (CMP) prepared in example 2, the test results are shown at 2100cm-1The peak is 1620cm generated by stretching vibration of carbon-nitrogen bond-1Is the peak generated by the stretching vibration of the benzene ring, 1520,1390 and 875cm-1A skeletal oscillation peak characteristic of the triazine ring can be observed, indicating that the chemical structure of the prepared Conjugated Microporous Polymer (CMP) is consistent with theoretical expectations.
Fig. 5 is a fluorescence emission spectrum of the quantum dot loaded conjugated microporous polymer (QD-CMP) provided in example 2 of the present invention at an excitation wavelength of 250nm, where the spectrum shows an intense peak at a wavelength of 450 nm, and is blue light emitted by the conjugated microporous polymer; a strong peak is also generated at the wavelength of 625 nanometers and is obtained under the excitation of red quantum dots, which shows that the red quantum dots loaded on the conjugated microporous polymer can be reasonably utilized; a strong peak appears at the wavelength of 532 nm, which is obtained under the excitation of green quantum dots, and shows that the green quantum dots loaded on the conjugated microporous polymer can be reasonably utilized.
Fig. 6 is a fluorescence emission spectrum of the green quantum dot loaded conjugated microporous polymer (GQD-CMP) at an excitation wavelength of 250nm, which shows an intense peak at a wavelength of 450 nm and is blue light emitted by the conjugated microporous polymer provided in example 11 of the present invention; a strong peak appears at the wavelength of 532 nm, which is obtained under the excitation of green quantum dots, and shows that the green quantum dots loaded on the conjugated microporous polymer can be reasonably utilized.
Fig. 7 is a fluorescence emission spectrum of a conjugated microporous polymer (RQD-CMP) supporting red quantum dots provided in example 12 of the present invention at an excitation wavelength of 250nm, where the spectrum shows an intense peak at a wavelength of 450 nm, and is blue light emitted from the conjugated microporous polymer; a strong peak is also generated at the wavelength of 625 nanometers and is obtained under the excitation of red quantum dots, which shows that the red quantum dots loaded on the conjugated microporous polymer can be reasonably utilized.
As shown in fig. 8, the quantum dot film 1 is disposed above the light guide plate 100, the prism sheet 2 is disposed above the quantum dot film 1, the polarizer 3 is disposed above the prism sheet 2, and the liquid crystal panel 4 is disposed above the polarizer 3. A direct type blue LED light source is disposed below the light guide plate 100, and a side type light source may be selected.
The specific surface area of the conjugated microporous polymer provided by the invention is large, and the yield of the conjugated microporous polymer is high; the prepared quantum dot-loaded conjugated microporous polymer composite material is high in loading rate and good in dispersibility; the quantum dot film provided by the invention has excellent optical performance. Wherein the specific surface area of the conjugated microporous polymer prepared in example 2 was 843m2The yield is 99 percent; the load rate of the quantum dot loaded conjugated microporous polymer composite material is 98%, and the dispersibility is good; the comprehensive performance is excellent. The quantum dot film prepared in example 10 has good optical properties, light transmittance of 93.33%, haze of 87.76%, and luminance of 3657cd/m2。
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (8)

1. A quantum dot-loaded conjugated microporous polymer, wherein the quantum dot is adsorbed on the surface of the conjugated microporous polymer, and the structural formula of a repeating unit in the conjugated microporous polymer is as follows:
Figure FDA0002495770680000011
the quantum dots are selected from green quantum dots, red quantum dots, or a mixture of the two.
2. The quantum dot-loaded conjugated microporous polymer according to claim 1, wherein the conjugated microporous polymer has a specific surface area of 267-843m2/g。
3. The quantum dot-loaded conjugated microporous polymer according to claim 1, wherein the quantum dots are composed of green quantum dots and red quantum dots.
4. The quantum dot-loaded conjugated microporous polymer according to claim 3, wherein the weight ratio of the green quantum dots to the red quantum dots is 1: 1.
5. a method of preparing the quantum dot-loaded conjugated microporous polymer of any one of claims 1 to 4, comprising the steps of:
(1) preparation of conjugated microporous polymer CMP: 1, 4-dicyanobenzene and zinc chloride powder are uniformly mixed and put into a quartz tube, then the quartz tube is vacuumized, fused and sealed, and is placed into a tube furnace to be heated for 20-80 hours at the temperature of 200-; after cooling to room temperature, taking out the powder in the quartz tube, and obtaining the required conjugate microporous polymer CMP after filtering, washing and Soxhlet extraction;
(2) preparing a quantum dot-loaded conjugated microporous polymer: fully stirring and uniformly mixing the quantum dot dispersion liquid and the conjugated microporous polymer, sealing the uniformly mixed slurry into a polytetrafluoroethylene hydrothermal reaction kettle, and placing the kettle in a high-temperature oven at 20-100 ℃ for 12 hours; and after cooling completely, carrying out suction filtration on the slurry, washing the slurry with deionized water, ethanol and chloroform, and carrying out vacuum drying at 60 ℃ to prepare the quantum dot-loaded conjugated microporous polymer QD-CMP.
6. The method for preparing the quantum dot-loaded conjugated microporous polymer according to claim 5, wherein the molar ratio of the 1, 4-dicyanobenzene to the zinc chloride powder in the step (1) is 1: 0.1-20.
7. A quantum dot membrane, comprising a quantum dot glue layer, wherein the quantum dot glue layer comprises the quantum dot-loaded conjugated microporous polymer according to any one of claims 1 to 4.
8. A liquid crystal display module comprising the quantum dot film of claim 7.
CN201810062789.1A 2018-01-23 2018-01-23 Quantum dot-loaded conjugated microporous polymer and preparation method thereof, quantum dot membrane and liquid crystal display module Active CN108373534B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810062789.1A CN108373534B (en) 2018-01-23 2018-01-23 Quantum dot-loaded conjugated microporous polymer and preparation method thereof, quantum dot membrane and liquid crystal display module

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810062789.1A CN108373534B (en) 2018-01-23 2018-01-23 Quantum dot-loaded conjugated microporous polymer and preparation method thereof, quantum dot membrane and liquid crystal display module

Publications (2)

Publication Number Publication Date
CN108373534A CN108373534A (en) 2018-08-07
CN108373534B true CN108373534B (en) 2020-09-01

Family

ID=63015605

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810062789.1A Active CN108373534B (en) 2018-01-23 2018-01-23 Quantum dot-loaded conjugated microporous polymer and preparation method thereof, quantum dot membrane and liquid crystal display module

Country Status (1)

Country Link
CN (1) CN108373534B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111196921A (en) * 2018-11-20 2020-05-26 苏州星烁纳米科技有限公司 Fluorescent nanomaterial-polymer complex, method for preparing wavelength conversion element, and light-emitting device
WO2022251197A1 (en) * 2021-05-24 2022-12-01 W. L. Gore & Associates, Inc. Dense photoluminescent composites and processes for fabricating the same

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102153186A (en) * 2011-05-11 2011-08-17 南京大学 Application of porous covalent triazine polymer for removing aromatic compound from water
CN105854937A (en) * 2016-05-04 2016-08-17 福州大学 Carbon quantum dot/CTF-T1 immobilized type visible light catalyst
CN107312522A (en) * 2017-07-06 2017-11-03 北京北达聚邦科技有限公司 A kind of high stability quantum dot fluorescence membrane preparation method

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9012770B2 (en) * 2011-05-26 2015-04-21 Brookhaven Science Associates, Llc Conductive polymer/fullerene blend thin films with honeycomb framework for transparent photovoltaic application

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102153186A (en) * 2011-05-11 2011-08-17 南京大学 Application of porous covalent triazine polymer for removing aromatic compound from water
CN105854937A (en) * 2016-05-04 2016-08-17 福州大学 Carbon quantum dot/CTF-T1 immobilized type visible light catalyst
CN107312522A (en) * 2017-07-06 2017-11-03 北京北达聚邦科技有限公司 A kind of high stability quantum dot fluorescence membrane preparation method

Also Published As

Publication number Publication date
CN108373534A (en) 2018-08-07

Similar Documents

Publication Publication Date Title
JP6332522B1 (en) Composition and method for producing the composition
CN109097038B (en) Solid yellow fluorescent carbon quantum dot and preparation method thereof
CN109652058B (en) Preparation method of carbon quantum dot and phosphorescent composite material thereof
Jin et al. Orange-red, green, and blue fluorescence carbon dots for white light emitting diodes
CN107828416B (en) Quantum dot fluorescent composite material and preparation method and application thereof
CN111393692A (en) Rapid and mild preparation method of covalent bonding room temperature phosphorescent film
KR20170012345A (en) Graphene quantum dot-polymer composites and methods of making the same
TWI782946B (en) Polymer composites and films comprising reactive additives having thiol groups for improved quantum dot dispersion and barrier properties
CN108373534B (en) Quantum dot-loaded conjugated microporous polymer and preparation method thereof, quantum dot membrane and liquid crystal display module
CN106032468A (en) Polymerizable quantum dot and application thereof
TWI791576B (en) Composition, film, laminated structure, light emitting device, and display
TW201910446A (en) Ink composition, film, and display
CN1772835A (en) Nanometer luminescent core-shell zinc oxide-polymer particle and its prepn
Yin et al. Yellow fluorescent graphene quantum dots as a phosphor for white tunable light-emitting diodes
CN110551304A (en) Cesium-lead halogen inorganic perovskite quantum dot/transparent polymer composite film
CN108484906B (en) Fluorenyl conjugated microporous polymer diffusion particle with quantum dots complexed and preparation method thereof, quantum dot diffusion film and application thereof
CN109233821B (en) Multicolor luminous carbon quantum dot and preparation method and application thereof
Wang et al. Fabrication of silver chalcogenolate cluster hybrid membranes with enhanced structural stability and luminescence efficiency
CN108072930A (en) A kind of light guide plate and its application with quantum dot diaphragm array and quantum dot site
Liu et al. A facile and universal strategy for preparation of long wavelength emission carbon dots
CN114162852A (en) Novel all-inorganic CsPbBr applied to LCD backlight display3Perovskite and preparation method thereof
CN113105351A (en) Electric polarization particle, preparation method thereof and application thereof in electric polarization color-changing optical film
CN113913186B (en) Carbon dot-based room-temperature phosphorescent composite material capable of stably emitting afterglow and preparation method, application and use method thereof
Enomoto et al. Highly luminescent MAPbI 3 perovskite quantum dots with a simple purification process via ultrasound-assisted bead milling
CN108384530B (en) Quantum dot-coated carbazolyl conjugated microporous polymer microsphere and preparation method thereof, quantum dot film and application 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