CN108384530B - Quantum dot-coated carbazolyl conjugated microporous polymer microsphere and preparation method thereof, quantum dot film and application thereof - Google Patents

Quantum dot-coated carbazolyl conjugated microporous polymer microsphere and preparation method thereof, quantum dot film and application thereof Download PDF

Info

Publication number
CN108384530B
CN108384530B CN201810095335.4A CN201810095335A CN108384530B CN 108384530 B CN108384530 B CN 108384530B CN 201810095335 A CN201810095335 A CN 201810095335A CN 108384530 B CN108384530 B CN 108384530B
Authority
CN
China
Prior art keywords
carbazolyl
quantum dot
microporous polymer
quantum dots
conjugated microporous
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
CN201810095335.4A
Other languages
Chinese (zh)
Other versions
CN108384530A (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 CN201810095335.4A priority Critical patent/CN108384530B/en
Publication of CN108384530A publication Critical patent/CN108384530A/en
Application granted granted Critical
Publication of CN108384530B publication Critical patent/CN108384530B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • 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
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/124—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one nitrogen atom in the ring
    • 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
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
    • C09K11/881—Chalcogenides
    • C09K11/883—Chalcogenides with zinc or cadmium
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/1336—Illuminating devices
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/11—Homopolymers
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/18—Definition of the polymer structure conjugated
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/22—Molecular weight
    • C08G2261/228—Polymers, i.e. more than 10 repeat units
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
    • C08G2261/3241—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more nitrogen atoms as the only heteroatom, e.g. carbazole
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/35—Macromonomers, i.e. comprising more than 10 repeat units
    • C08G2261/354—Macromonomers, i.e. comprising more than 10 repeat units containing hetero atoms
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/40—Polymerisation processes
    • C08G2261/43—Chemical oxidative coupling reactions, e.g. with FeCl3
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/50—Physical properties
    • C08G2261/52—Luminescence
    • C08G2261/522—Luminescence fluorescent
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/1336—Illuminating devices
    • G02F1/133614—Illuminating devices using photoluminescence, e.g. phosphors illuminated by UV or blue light

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Nonlinear Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Optics & Photonics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mathematical Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Luminescent Compositions (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention relates to a quantum dot film, in particular to a carbazolyl conjugated microporous polymer microsphere wrapping quantum dots, a preparation method thereof, a quantum dot film and application thereof. In order to solve the problems of low blue light purity and low blue light utilization efficiency in the use of the existing quantum dot and solve the problems of low light transmittance and poor stability of the existing quantum dot film, the invention provides a carbazolyl conjugated microporous polymer microsphere wrapping quantum dots, a preparation method thereof, a quantum dot film and application thereof. The quantum dots are distributed in the carbazolyl conjugated microporous polymer microspheres. The carbazolyl conjugated microporous polymer microspheres wrapping the quantum dots can effectively solve the problem that the quantum dots have low utilization efficiency of blue light, improve the purity of the blue light and prevent the quantum dots from being oxidized by oxygen and water vapor in the air; therefore, the quantum dot film provided by the invention has excellent optical performance.

Description

Quantum dot-coated carbazolyl conjugated microporous polymer microsphere and preparation method thereof, quantum dot film and application thereof
Technical Field
The invention relates to a quantum dot film, in particular to a carbazolyl conjugated microporous polymer microsphere wrapping quantum dots, a preparation method thereof, a quantum dot film and application thereof.
Background
Quantum dots are three-dimensional clusters of nanometer-scale dimensions and are therefore also referred to as nanodots or nanocrystals. Due to the special structure of the quantum dot, the quantum dot has a quantum size effect, a macroscopic quantum tunneling effect, a dielectric confinement effect and a surface effect, so that unique physical and chemical properties and specific luminous performance are generated, and the quantum dot material becomes a cross field relating to multiple disciplines such as physics and chemistry, optics, nano material technology and the like. With the rapid development of semiconductor quantum dot synthesis, the semiconductor quantum dot has the advantages of low cost, strong stability, high quantum yield, large-scale production and the like, so that the semiconductor quantum dot is considered as a solid foundation for further research on a plurality of leading-edge applications. Especially, 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, 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 of quantum dots: 1) 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. 2) At present, the utilization rate of blue light emitted by a backlight source is relatively low due to red and green quantum dots, and the fluorescence quantum efficiency of the backlight source cannot be effectively exerted. 3) The blue backlight excites the quantum dots to provide red and green colors, the purity of the red and green colors is higher than that of a common television using a white light source, and therefore, the red and green colors are brighter, but the blue light is directly obtained from the backlight, and therefore, the purity of the blue light is lower. Problems (2) and (3) both affect the color gamut coverage of the backlight module.
Carbazole is a nitrogen-containing aromatic heterocycle with a unique rigid condensed ring structure, and organic small molecules and polymers containing carbazole groups show good photoelectric properties and are widely applied to the field of organic photoelectric materials. The structure of the carbazole material has the following characteristics: 1) the molecule has a larger conjugated system and strong intramolecular electron transfer, so that the luminescent material has good luminescent property; 2) the rigid condensed ring has higher thermal and oxygen stability; 3) the N atom in the carbazole molecule has a delocalized lone pair of electrons, and can play a role in shielding oxygen molecules by charges.
Therefore, the problem of low utilization rate of blue light of the inorganic quantum dots can be effectively solved by combining the advantages of the organic carbazole materials into the optical application of the inorganic quantum dot materials.
Disclosure of Invention
In order to solve the problems of low purity of blue light and low utilization efficiency of the blue light by quantum dots in the prior art, the invention provides a carbazolyl conjugated microporous polymer microsphere wrapping the quantum dots, a preparation method thereof, a quantum dot film and application thereof. On the other hand, in order to solve the problems of low light transmittance and poor stability of the conventional quantum dot film, the invention provides a carbazolyl conjugated microporous polymer microsphere wrapping quantum dots, a preparation method thereof, a quantum dot film and application thereof. The carbazolyl conjugated microporous polymer microspheres wrapping the quantum dots can effectively solve the problem that the quantum dots have low utilization efficiency of blue light, improve the purity of the blue light and prevent the quantum dots from being oxidized by oxygen and water vapor in the air; therefore, the quantum dot film provided by the invention has excellent optical performance.
In order to solve the technical problems, the invention provides the following technical scheme:
the invention provides a carbazolyl conjugated microporous polymer microsphere wrapping quantum dots, wherein the quantum dots are distributed in the carbazolyl conjugated microporous polymer microsphere.
Further, the diameter of the carbazolyl conjugated microporous polymer microsphere wrapping the quantum dots is 50-750 nm.
Further, the diameter of the carbazolyl conjugated microporous polymer microspheres wrapping the quantum dots is preferably 150 nm.
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.
The green quantum dots are selected from green cadmium selenide quantum dots, and the red quantum dots are selected from red cadmium selenide quantum dots.
Further, the quantum dots are composed of green quantum dots and red quantum dots.
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. The mass ratio of the two can be adjusted according to the specific optical display performance requirement.
Further, the weight ratio of the green quantum dots to the red quantum dots is 1: 1.
the invention also provides a preparation method of the carbazolyl conjugated microporous polymer microspheres wrapping the quantum dots, which comprises the following steps:
(1) adding a proper amount of ferric trichloride powder into an ethanol solution dissolved with sodium citrate and cadmium selenide quantum dots, then dropwise adding a chloroform solution dissolved with carbazolyl monomers, and reacting at room temperature for 24 hours;
(2) filtering, washing and Soxhlet extracting to obtain the carbazolyl conjugated microporous polymer microsphere wrapping the quantum dots.
Further, the carbazolyl monomer is 1, 4-bis (9-carbazole) benzene.
Further, the reaction equation of the carbazolyl conjugated microporous polymer microspheres is as follows:
Figure BDA0001564891190000041
asterisks in the structural formula of the above reaction product represent repeating units.
Further, the preparation method of the carbazolyl conjugated microporous polymer microspheres wrapping the quantum dots comprises the following steps: after the nitrogen gas is pumped into a 250mL three-mouth bottle, FeCl is quickly weighed and added3And chloroform. Then adding an ethanol solution dissolved with cadmium selenide quantum dots and sodium citrate, slowly dropwise adding a chloroform solution dissolved with 1g of 1, 4-di (9-carbazole) benzene by using a syringe, and starting stirring. Reacting at room temperature for 24 hours, adding 300mL of methanol, stirring for 1 hour, carrying out suction filtration, eluting with methanol, concentrated hydrochloric acid and deionized water for 1 time respectively, and finally carrying out respective Soxhlet extraction (Soxhlet extraction) with methanol and tetrahydrofuran for 24 hours to obtain a crude product. Finally vacuum drying at 60 deg.C for 12 hr to obtain yellow powder as the carbo coated with quantum dotsAzole-based conjugated microporous polymer microspheres.
Further, the feeding ratio of the carbazolyl monomer to the ferric chloride is 1: 0.2-20.
The charging ratio refers to the weight ratio of the added raw materials. Ferric trichloride is the reaction catalyst.
Further, the purity requirement of the ferric trichloride is 99.9%; the feeding ratio of the carbazolyl monomer and the ferric chloride can be adjusted according to the requirement of the specific surface area of the needed polymer.
Further, the feeding ratio of the carbazolyl monomer to the cadmium selenide quantum dot is 1: 0.1-10.
Furthermore, the feeding ratio of the carbazolyl monomer and the cadmium selenide quantum dot can be adjusted according to the requirement of the optical performance of the required material.
Further, the feeding ratio of the carbazolyl monomer to the sodium citrate is 1: 0.1-10.
The sodium citrate is used for adjusting the pH value of the reaction system, and the feeding ratio of the carbazolyl monomer to the sodium citrate can be adjusted according to the requirement of the volume of the needed microspheres.
Further, the feeding ratio of the carbazolyl monomer to the ferric chloride is 1: 2, the feeding ratio of the carbazolyl monomer to the cadmium selenide quantum dot is 1: 1, the feeding ratio of the carbazolyl monomer to the sodium citrate is 1: 1.
the invention also provides a quantum dot film, which comprises a quantum dot adhesive layer, wherein the quantum dot adhesive layer comprises carbazolyl conjugated microporous polymer microspheres wrapping the quantum dots.
The invention also provides a preparation method of the quantum dot film, which comprises the following steps: uniformly stirring the conjugated microporous polymer wrapping the quantum dots and the acrylate UV curing adhesive to form a coating liquid of a quantum dot adhesive layer, uniformly coating the coating liquid on the surface of a PET film, and curing by a UV lamp to obtain the quantum dot film.
The invention also provides an application of the quantum dot film, and the quantum dot film is used for a liquid crystal display module.
The quantum dot membrane prepared by the carbazolyl conjugated microporous polymer microspheres wrapping the quantum dots is applied to the field of display equipment.
Furthermore, the liquid crystal display module sequentially comprises a light source, a light guide plate, a quantum dot film, 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:
(1) the conjugated microporous polymer microsphere provided by the invention is internally wrapped with red and green quantum dots, so that the introduction of a single white dot is realized on a smaller scale, and the pixel of the display equipment is greatly improved.
(2) The purity of blue light excited by the polymer microspheres in the quantum dot-coated conjugated microporous polymer microspheres is higher than that of a blue backlight source, so that the purity of the blue light excited by the quantum dots is improved; the coated quantum dots can diffuse and reflect blue light excited by the polymer microspheres for multiple times in the microspheres, so that the utilization efficiency of the quantum dots on the blue light is improved; the prepared quantum dot film can reduce the actual using amount of quantum dots, namely reduce the cost and simultaneously improve the overall optical performance of a system.
(3) The invention uses organic conjugated microporous polymer microspheres with large specific surface area to wrap inorganic quantum dots, fundamentally overcomes the defect of poor compatibility of the existing inorganic quantum dots and organic polymer glue systems, and avoids unstable factors such as uneven dispersion, difficult control of membrane thickness, large color coordinate offset and the like in the production process caused by system incompatibility.
(4) The microporous polymer microspheres provided by the invention shield the adverse effects of water and oxygen on the stability of the quantum dots, and the formula has good stability under harsh aging conditions (high temperature, high humidity and strong blue light), so that the characteristic that the optical performance of the quantum dots is reduced due to instability can be effectively prevented, and the normal service life of display equipment is greatly prolonged.
(5) The process of the quantum dot-coated conjugated microporous polymer microspheres and the quantum dot film provided by the invention is simple, and the raw materials are cheap and easy to obtain, so that the quantum dot-coated conjugated microporous polymer microspheres and the quantum dot film have wide application capability and feasibility of mass production.
(6) The quantum dot film provided by the invention has high light transmittance and good stability.
Drawings
FIG. 1 is a schematic structural diagram of a carbazolyl conjugated microporous polymer microsphere coated with quantum dots, provided by the invention;
FIG. 2 is a synthesis scheme of carbazolyl conjugated microporous polymer microspheres provided by the present invention;
fig. 3 is a scanning electron microscope image of the quantum dot-coated carbazolyl conjugated microporous polymer microsphere prepared in example 1 of the present invention;
FIG. 4 is a Fourier infrared spectrum of the quantum dot coated carbazolyl conjugated microporous polymer microsphere prepared in example 1 of the present invention;
fig. 5 is a fluorescence emission spectrum of the carbazolyl conjugated microporous polymer microspheres coated with red and green quantum dots prepared in example 1 of the present invention;
FIG. 6 is a diagram of the UV-VIS absorption spectrum of the carbazolyl conjugated microporous polymer microspheres coated with red and green quantum dots prepared in example 1 of the present invention;
fig. 7 is a schematic structural diagram of a 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 carbazolyl conjugated microporous polymer microspheres wrapping the quantum dots, provided by the invention, comprises the following steps:
(1) preparation of the carbazolyl conjugated microporous polymer microspheres wrapping the quantum dots, adding a proper amount of ferric trichloride powder into an ethanol solution in which sodium citrate and cadmium selenide quantum dots are dissolved, then dropwise adding a chloroform solution in which carbazolyl monomers are dissolved, and finally cooling at room temperature for 24 hours;
(2) filtering, washing and Soxhlet extracting to obtain the carbazolyl conjugated microporous polymer microsphere wrapping the quantum dots.
The invention also provides a preparation method of the quantum dot film, which comprises the following steps: uniformly stirring carbazolyl conjugated microporous polymer microspheres wrapping the quantum dots and acrylate UV curing adhesive to form coating liquid of a quantum dot adhesive layer, uniformly coating the coating liquid on the surface of a PET film, and curing by a UV lamp to obtain the quantum dot film.
Fig. 1 is a schematic structural diagram of the carbazolyl conjugated microporous polymer microsphere coated with quantum dots, wherein green cadmium selenide quantum dots 1 and red cadmium selenide quantum dots 2 are coated in a carbazolyl conjugated microporous polymer microsphere 3.
As shown in fig. 7, 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 related properties of the carbazolyl conjugated microporous polymer microspheres coated with quantum dots provided by the invention were tested in the following manner, and the results are shown in table 1.
1. Wrapping rate
Collecting and centrifuging the suction filtration liquid in the experiment step (2), removing supernatant, drying and weighing to obtain the mass of the cadmium selenide quantum dots which are not wrapped in the microspheres;
the encapsulation ratio is (total mass of reaction input quantum dots-mass of quantum dots obtained after centrifugation)/total mass of reaction input quantum dots.
2. Reaction yield
The reaction yield (mass-encapsulation ratio of the carbazolyl conjugated microporous polymer microsphere encapsulating the quantum dot x total mass of the quantum dot charged in the reaction)/total mass of the monomer charged in the reaction.
3. Dispersibility
5g of prepared carbazolyl conjugated microporous polymer microspheres wrapping quantum dots are added into 100ml of IBOA solution and mechanically stirred for 30min, and then the mixture is stood and the settlement condition is observed. The evaluation 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.
4. Specific surface area
150mg of the sample is loaded into a nitrogen adsorption instrument, the nitrogen adsorption condition of the sample is tested in a liquid nitrogen atmosphere, and the nitrogen adsorption condition is automatically converted into the specific surface area.
5. Diameter of microsphere
The resulting sample was observed under a scanning electron microscope and the average diameter of the microspheres was measured.
The main optical properties of the quantum dot thin film 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 measure the light transmittance or haze value.
2. Testing brightness and color gamut: a 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 provided by the invention), and is lightened under the voltage of 24V, and the luminance and the color gamut coverage rate of the quantum dot film are tested by using a luminance instrument (CS-2000). Higher luminance indicates higher brightness; higher gamut coverage indicates higher color contrast.
3. The optical evaluation criteria are as follows:
stability: the luminance retention ratio comprises a luminance retention ratio at high temperature, a luminance retention ratio at high temperature and high humidity and a luminance retention ratio at blue light; aging the prepared quantum dot film in a high-temperature oven at 80 ℃, a high-temperature high-humidity box at 80 ℃/95% humidity and a strong blue light box at 70 times, and testing the brightness after aging, wherein the brightness retention rate is the brightness after aging/the brightness before aging; the higher the luminance retention rate, the better the stability of the quantum dot film. The evaluation criteria are as follows:
excellent: the brightness retention rate is more than or equal to 95 percent;
in general: the luminance retention rate is more than or equal to 85 percent and less than 95 percent;
poor results are obtained: the luminance retention rate is less than or equal to 80 percent.
Optical properties: a summary of the overall performance of the film includes color gamut coverage, luminance and transmittance.
Excellent: the light transmittance of the film surface is more than 90 percent (inclusive), the color gamut coverage rate is more than or equal to 108 percent, and the luminance before aging is more than or equal to 3500cd/m2；
In general: the light transmittance of the film surface is more than 90 percent (inclusive), the color gamut coverage rate is more than 101 percent and less than 108 percent, 3000cd/m2The luminance before aging is less than or equal to 3500cd/m2；
Poor results are obtained: the light transmittance of the film surface is more than 90 percent (inclusive), the color gamut coverage rate is less than or equal to 100 percent, and the luminance before aging is less than or equal to 2800cd/m2。
Example 1
The invention provides a carbazolyl conjugated microporous polymer microsphere wrapping quantum dots, wherein the quantum dots are distributed in the carbazolyl conjugated microporous polymer microsphere.
After the nitrogen gas was purged from a 250mL three-necked flask, 2g of FeCl was quickly weighed and added3And 30mL of chloroform. Then 20mL of an ethanol solution containing 0.5g of red cadmium selenide, 0.5g of green cadmium selenide and 1g of sodium citrate was added, and 50mL of a chloroform solution containing 1g of 1, 4-bis (9-carbazole) benzene was slowly dropped by a syringe, and stirring was started. Reacting at room temperature for 24 hours, adding 300mL of methanol, stirring for 1 hour, performing suction filtration, leaching for 1 time by using methanol, concentrated hydrochloric acid and deionized water respectively, and finally performing soxhlet extraction for 24 hours by using methanol and tetrahydrofuran respectively to obtain a crude product. And finally, vacuum drying for 12 hours at 60 ℃ to obtain 1.97g of yellow powder, namely the carbazolyl conjugated microporous polymer microspheres wrapping the quantum dots.
The performance test results of the prepared carbazolyl conjugated microporous polymer microspheres wrapping the quantum dots are shown in table 1.
Example 2
The quantum dot-encapsulated carbazolyl conjugated microporous polymer microspheres as provided in example 1.
After the nitrogen is pumped and changed for a three-mouth bottle of 250mL, the nitrogen is quickly changedQuickly weighing and adding 2g FeCl3And 30mL of chloroform. Then 20mL of an ethanol solution containing 0.5g of red cadmium selenide, 0.5g of green cadmium selenide and 0.1g of sodium citrate was added, and 50mL of a chloroform solution containing 1g of 1, 4-bis (9-carbazole) benzene was slowly dropped by a syringe, and stirring was started. Reacting at room temperature for 24 hours, adding 300mL of methanol, stirring for 1 hour, performing suction filtration, leaching for 1 time by using methanol, concentrated hydrochloric acid and deionized water respectively, and finally performing soxhlet extraction for 24 hours by using methanol and tetrahydrofuran respectively to obtain a crude product. And finally, vacuum drying for 12 hours at 60 ℃ to obtain 1.67g of yellow powder, namely the carbazolyl conjugated microporous polymer microspheres wrapping the quantum dots.
The performance test results of the prepared carbazolyl conjugated microporous polymer microspheres wrapping the quantum dots are shown in table 1.
Example 3
The quantum dot-encapsulated carbazolyl conjugated microporous polymer microspheres as provided in example 1.
After the nitrogen gas was purged from a 250mL three-necked flask, 2g of FeCl was quickly weighed and added3And 30mL of chloroform. Then 20mL of an ethanol solution containing 0.5g of red cadmium selenide, 0.5g of green cadmium selenide and 10g of sodium citrate was added, and 50mL of a chloroform solution containing 1g of 1, 4-bis (9-carbazole) benzene was slowly dropped by a syringe, and stirring was started. Reacting at room temperature for 24 hours, adding 300mL of methanol, stirring for 1 hour, performing suction filtration, leaching for 1 time by using methanol, concentrated hydrochloric acid and deionized water respectively, and finally performing soxhlet extraction for 24 hours by using methanol and tetrahydrofuran respectively to obtain a crude product. And finally, vacuum drying for 12 hours at 60 ℃ to obtain 1.95g of yellow powder, namely the carbazolyl conjugated microporous polymer microspheres coated with the quantum dots.
The performance test results of the prepared carbazolyl conjugated microporous polymer microspheres wrapping the quantum dots are shown in table 1.
Example 4
The quantum dot-encapsulated carbazolyl conjugated microporous polymer microspheres as provided in example 1.
After the nitrogen gas was purged from a 250mL three-necked flask, 0.2g of FeCl was quickly weighed and added3And 30mL of chloroform. Then 20mL of an ethanol solution containing 0.5g of red cadmium selenide, 0.5g of green cadmium selenide and 1g of sodium citrate was added, and the mixture was slowly injected with a syringe50mL of a chloroform solution containing 1g of 1, 4-bis (9-carbazole) benzene was added dropwise thereto, and stirring was started. Reacting at room temperature for 24 hours, adding 300mL of methanol, stirring for 1 hour, performing suction filtration, leaching for 1 time by using methanol, concentrated hydrochloric acid and deionized water respectively, and finally performing soxhlet extraction for 24 hours by using methanol and tetrahydrofuran respectively to obtain a crude product. And finally, vacuum drying for 12 hours at 60 ℃ to obtain 1.85g of yellow powder, namely the carbazolyl conjugated microporous polymer microspheres coated with the quantum dots.
The performance test results of the prepared carbazolyl conjugated microporous polymer microspheres wrapping the quantum dots are shown in table 1.
Example 5
The quantum dot-encapsulated carbazolyl conjugated microporous polymer microspheres as provided in example 1.
After the nitrogen gas was purged from a 250mL three-necked flask, 20g of FeCl was quickly weighed and added3And 30mL of chloroform. Then 20mL of an ethanol solution containing 0.5g of red cadmium selenide, 0.5g of green cadmium selenide and 1g of sodium citrate was added, and 50mL of a chloroform solution containing 1g of 1, 4-bis (9-carbazole) benzene was slowly dropped by a syringe, and stirring was started. Reacting at room temperature for 24 hours, adding 300mL of methanol, stirring for 1 hour, performing suction filtration, leaching for 1 time by using methanol, concentrated hydrochloric acid and deionized water respectively, and finally performing soxhlet extraction for 24 hours by using methanol and tetrahydrofuran respectively to obtain a crude product. And finally, vacuum drying for 12 hours at 60 ℃ to obtain 1.72g of yellow powder, namely the carbazolyl conjugated microporous polymer microspheres coated with the quantum dots.
The performance test results of the prepared carbazolyl conjugated microporous polymer microspheres wrapping the quantum dots are shown in table 1.
Example 6
The quantum dot-encapsulated carbazolyl conjugated microporous polymer microspheres as provided in example 1.
After the nitrogen gas was purged from a 250mL three-necked flask, 2g of FeCl was quickly weighed and added3And 30mL of chloroform. Then 20mL of an ethanol solution containing 0.05g of red cadmium selenide, 0.05g of green cadmium selenide and 1g of sodium citrate was added, and 50mL of a chloroform solution containing 1g of 1, 4-bis (9-carbazole) benzene was slowly dropped by a syringe, and stirring was started. Reacting at room temperature for 24 hours, adding 300mL of methanol, stirring for 1 hour, filtering by suction, and removing by using methanol, concentrated hydrochloric acidEluting with ionized water for 1 time respectively, and finally carrying out soxhlet extraction with methanol and tetrahydrofuran respectively for 24 hours to obtain a crude product. And finally, vacuum drying for 12 hours at 60 ℃ to obtain 1.097g of yellow powder, namely the carbazolyl conjugated microporous polymer microspheres coated with the quantum dots.
The performance test results of the prepared carbazolyl conjugated microporous polymer microspheres wrapping the quantum dots are shown in table 1.
Example 7
The quantum dot-encapsulated carbazolyl conjugated microporous polymer microspheres as provided in example 1.
After the nitrogen gas was purged from a 250mL three-necked flask, 2g of FeCl was quickly weighed and added3And 30mL of chloroform. Then 20mL of an ethanol solution containing 5g of red cadmium selenide, 5g of green cadmium selenide and 1g of sodium citrate was added, and 50mL of a chloroform solution containing 1g of 1, 4-bis (9-carbazole) benzene was slowly dropped by using a syringe, and stirring was started. Reacting at room temperature for 24 hours, adding 300mL of methanol, stirring for 1 hour, performing suction filtration, leaching for 1 time by using methanol, concentrated hydrochloric acid and deionized water respectively, and finally performing soxhlet extraction for 24 hours by using methanol and tetrahydrofuran respectively to obtain a crude product. And finally, vacuum drying for 12 hours at 60 ℃ to obtain 7.98g of yellow powder, namely the carbazolyl conjugated microporous polymer microspheres wrapping the quantum dots.
The performance test results of the prepared carbazolyl conjugated microporous polymer microspheres wrapping the quantum dots are shown in table 1.
Example 8
The invention provides a quantum dot film which comprises a quantum dot adhesive layer, wherein the quantum dot adhesive layer comprises carbazolyl conjugated microporous polymer microspheres wrapping quantum dots.
Weighing 25g of the quantum dot-coated carbazolyl conjugated microporous polymer microspheres prepared in example 1 and 100g of isobornyl acrylate (IBOA) and uniformly stirring on a vibrator, adding the mixture into 1000g of acrylate UV curing adhesive mixed solution, mechanically stirring for 2 hours, and standing to obtain the quantum dot adhesive.
And (3) injecting the uniformly mixed quantum dot glue into a die head through a screw pump, uniformly coating the glue on the surface of PET, and performing rolling, ultraviolet irradiation curing and cutting to obtain a quantum dot diaphragm with the size of A4, wherein the thickness of the glue layer is 50 microns.
The results of the performance tests of the prepared quantum dot films are shown in table 2.
Example 9
The quantum dot film as provided in example 8.
Weighing 25g of the quantum dot-coated carbazolyl conjugated microporous polymer microspheres prepared in example 4 and 100g of isobornyl acrylate (IBOA) and uniformly stirring on a vibrator, adding the mixture into 1000g of acrylate UV curing adhesive mixed solution, mechanically stirring for 2 hours, and standing to obtain the quantum dot adhesive.
And (3) injecting the uniformly mixed quantum dot glue into a die head through a screw pump, uniformly coating the glue on the surface of PET, and performing rolling, ultraviolet irradiation curing and cutting to obtain a quantum dot diaphragm with the size of A4, wherein the thickness of the glue layer is 50 microns.
The results of the performance tests of the prepared quantum dot films are shown in table 2.
Example 10
The quantum dot film as provided in example 8.
Weighing 25g of the quantum dot-coated carbazolyl conjugated microporous polymer microspheres prepared in example 5 and 100g of isobornyl acrylate (IBOA) and uniformly stirring on a vibrator, adding the mixture into 1000g of acrylate UV curing adhesive mixed solution, mechanically stirring for 2 hours, and standing to obtain the quantum dot adhesive.
And (3) injecting the uniformly mixed quantum dot glue into a die head through a screw pump, uniformly coating the glue on the surface of PET, and performing rolling, ultraviolet irradiation curing and cutting to obtain a quantum dot diaphragm with the size of A4, wherein the thickness of the glue layer is 50 microns.
The results of the performance tests of the prepared quantum dot films are shown in table 2.
Comparative example 1
The quantum dot-encapsulated carbazolyl conjugated microporous polymer microspheres as provided in example 1.
After the nitrogen gas was purged from a 250mL three-necked flask, 2g of FeCl was quickly weighed and added3And 30mL of chloroform. Then 20mL of ethanol solution containing 0.5g of red cadmium selenide, 0.5g of green cadmium selenide and 0.01g of sodium citrate is added, 50mL of chloroform solution containing 1g of 1, 4-bis (9-carbazole) benzene is slowly dropped by a syringe, and stirring is started. Reacting at room temperature for 24 hours, adding 300mL of methanol, stirring for 1 hour, performing suction filtration, leaching for 1 time by using methanol, concentrated hydrochloric acid and deionized water respectively, and finally performing soxhlet extraction for 24 hours by using methanol and tetrahydrofuran respectively to obtain a crude product. And finally, vacuum drying for 12 hours at 60 ℃ to obtain 1.18g of yellow powder, namely the carbazolyl conjugated microporous polymer microspheres wrapping the quantum dots.
The performance test results of the prepared carbazolyl conjugated microporous polymer microspheres wrapping the quantum dots are shown in table 1.
Comparative example 2
The quantum dot-encapsulated carbazolyl conjugated microporous polymer microspheres as provided in example 1.
After the nitrogen gas was purged from a 250mL three-necked flask, 2g of FeCl was quickly weighed and added3And 30mL of chloroform. Then 20mL of an ethanol solution containing 0.5g of red cadmium selenide, 0.5g of green cadmium selenide and 15g of sodium citrate was added, and 50mL of a chloroform solution containing 1g of 1, 4-bis (9-carbazole) benzene was slowly dropped by a syringe, and stirring was started. Reacting at room temperature for 24 hours, adding 300mL of methanol, stirring for 1 hour, performing suction filtration, leaching for 1 time by using methanol, concentrated hydrochloric acid and deionized water respectively, and finally performing soxhlet extraction for 24 hours by using methanol and tetrahydrofuran respectively to obtain a crude product. And finally, vacuum drying for 12 hours at 60 ℃ to obtain 1.95g of yellow powder, namely the carbazolyl conjugated microporous polymer microspheres coated with the quantum dots.
The performance test results of the prepared carbazolyl conjugated microporous polymer microspheres wrapping the quantum dots are shown in table 1.
Comparative example 3
The quantum dot-encapsulated carbazolyl conjugated microporous polymer microspheres as provided in example 1.
After the nitrogen gas was purged from a 250mL three-necked flask, 0.1g of FeCl was quickly weighed and added3And 30mL of chloroform. Then 20mL of an ethanol solution containing 0.5g of red cadmium selenide, 0.5g of green cadmium selenide and 1g of sodium citrate was added, and 50mL of a chloroform solution containing 1g of 1, 4-bis (9-carbazole) benzene was slowly dropped by a syringe, and stirring was started. Reacting at room temperature for 24 hours, adding 300mL of methanol, stirring for 1 hour, filtering, leaching with methanol, concentrated hydrochloric acid and deionized water for 1 time respectively, and finally respectively extracting with methanol and tetrahydrofuran for 24 hoursAfter a while, a crude product was obtained. And finally, vacuum drying for 12 hours at 60 ℃ to obtain 0.44g of yellow powder, namely the carbazolyl conjugated microporous polymer microspheres coated with the quantum dots.
The performance test results of the prepared carbazolyl conjugated microporous polymer microspheres wrapping the quantum dots are shown in table 1.
Comparative example 4
The quantum dot-encapsulated carbazolyl conjugated microporous polymer microspheres as provided in example 1.
After the nitrogen gas was purged from a 250mL three-necked flask, 50g of FeCl was quickly weighed and added3And 30mL of chloroform. Then 20mL of an ethanol solution containing 0.5g of red cadmium selenide, 0.5g of green cadmium selenide and 1g of sodium citrate was added, and 50mL of a chloroform solution containing 1g of 1, 4-bis (9-carbazole) benzene was slowly dropped by a syringe, and stirring was started. Reacting at room temperature for 24 hours, adding 300mL of methanol, stirring for 1 hour, performing suction filtration, leaching for 1 time by using methanol, concentrated hydrochloric acid and deionized water respectively, and finally performing soxhlet extraction for 24 hours by using methanol and tetrahydrofuran respectively to obtain a crude product. And finally, vacuum drying for 12 hours at 60 ℃ to obtain 0.55g of yellow powder, namely the carbazolyl conjugated microporous polymer microspheres coated with the quantum dots.
The performance test results of the prepared carbazolyl conjugated microporous polymer microspheres wrapping the quantum dots are shown in table 1.
Comparative example 5
The quantum dot-encapsulated carbazolyl conjugated microporous polymer microspheres as provided in example 1.
After the nitrogen gas was purged from a 250mL three-necked flask, 2g of FeCl was quickly weighed and added3And 30mL of chloroform. Then 20mL of an ethanol solution in which 15g of red cadmium selenide, 15g of green cadmium selenide and 1g of sodium citrate were dissolved was added, and 50mL of a chloroform solution in which 1g of 1, 4-bis (9-carbazole) benzene was dissolved was slowly dropped by a syringe, and stirring was started. Reacting at room temperature for 24 hours, adding 300mL of methanol, stirring for 1 hour, performing suction filtration, leaching for 1 time by using methanol, concentrated hydrochloric acid and deionized water respectively, and finally performing soxhlet extraction for 24 hours by using methanol and tetrahydrofuran respectively to obtain a crude product. And finally, vacuum drying for 12 hours at 60 ℃ to obtain 5.79g of yellow powder, namely the carbazolyl conjugated microporous polymer microspheres coated with the quantum dots.
The performance test results of the prepared carbazolyl conjugated microporous polymer microspheres wrapping the quantum dots are shown in table 1.
Comparative example 6
The quantum dot film as provided in example 8.
Weighing 25g of the quantum dot-coated carbazolyl conjugated microporous polymer microspheres prepared in the comparative example 2 and 100g of isobornyl acrylate (IBOA) to be uniformly stirred on a vibrator, adding the mixture into 1000g of mixed solution of acrylate UV curing adhesive, mechanically stirring for 2 hours, and standing to obtain the quantum dot glue.
And (3) injecting the uniformly mixed quantum dot glue into a die head through a screw pump, uniformly coating the glue on the surface of PET, and performing rolling, ultraviolet irradiation curing and cutting to obtain a quantum dot diaphragm with the size of A4, wherein the thickness of the glue layer is 50 microns.
The results of the performance tests of the prepared quantum dot films are shown in table 2.
The carbazolyl conjugated microporous polymer microspheres wrapped with quantum dots prepared in example 1 were subjected to a relevant structural characterization test, and the test results were as follows:
fig. 3 is a scanning electron microscope image of the carbazolyl conjugated microporous polymer microsphere coated with quantum dots prepared in example 1, and a test result shows that the obtained material is a rough porous microsphere with a substance contained therein.
FIG. 4 is a Fourier infrared spectrum of the carbazolyl conjugated microporous polymer microspheres coated with quantum dots prepared in example 1, at 1400-1550 cm -1700 to 850cm-1The vibration absorption peak appeared in the area indicates that the benzene ring structure exists in the prepared material. In the range of 1200-1300 cm-1The C-N stretching vibration absorption peak appears at the position of the polymer, and is derived from carbazole units in the polymer. The results show that the chemical structure of the prepared carbazolyl conjugated microporous polymer microsphere wrapping the quantum dots is consistent with theoretical expectation.
Fig. 5 is a fluorescence emission spectrum of the quantum dot-coated carbazolyl conjugated microporous polymer microsphere provided in embodiment 1 of the present invention at an excitation wavelength of 250nm, where the spectrum has an intense peak at a wavelength of 448nm and is blue light emitted by the conjugated microporous polymer; a strong peak appears at the wavelength of 531nm and is obtained under the excitation of green quantum dots, which shows that the carbazolyl conjugated microporous polymer microspheres can reasonably utilize the wrapped green quantum dots; a strong peak is also generated at the wavelength of 624nm and is obtained under the excitation of red quantum dots, which shows that the carbazolyl conjugated microporous polymer microspheres can reasonably utilize the wrapped red quantum dots.
Fig. 6 is a uv-vis absorption spectrum of the carbazolyl conjugated microporous polymer encapsulating quantum dots provided in example 1 of the present invention. As can be seen from the spectrogram, two absorption peaks appear at the wavelengths of 470-530nm and 580-620nm, which indicates that the carbazolyl conjugated microporous polymer microspheres coating the quantum dots can absorb red light and green light; when the wavelength is less than 450nm, the absorption strength of the material is obviously enhanced, which shows that the carbazolyl conjugated microporous polymer microspheres wrapping the quantum dots have strong absorption on electromagnetic waves with the wavelength less than or equal to the blue light wavelength, and the material can effectively utilize a backlight source.
Table 1 results of performance test of carbazolyl conjugated microporous polymer microspheres coated with quantum dots provided in examples 1 to 7 and comparative examples 1 to 5
Figure BDA0001564891190000211
Table 2 results of optical property test of quantum dot thin films provided in examples 8 to 10 and comparative example 6
Figure BDA0001564891190000212
Figure BDA0001564891190000221
The carbazolyl conjugated microporous polymer microspheres coated with the quantum dots provided by the invention have good specific surface area, dispersibility, yield and coating rate, and good comprehensive properties: specific surface area of 358-2The yield is at least 82%, the wrapping rate is at least 70%, and the dispersity is at least general; the quantum dot film provided by the invention has good optical performance and stability. In particular, example 1 provides for encapsulating quantum dotsThe carbazolyl conjugated microporous polymer microsphere has better comprehensive performance: specific surface area is 767m2The production rate is 99 percent, the wrapping rate is 98 percent, and the dispersibility is good. The quantum dot film provided in example 8 has better overall properties: excellent optical performance and stability.
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 (10)

1. The carbazolyl conjugated microporous polymer microspheres coated with the quantum dots are characterized in that the quantum dots are distributed in the carbazolyl conjugated microporous polymer microspheres; the carbazolyl conjugated microporous polymer has the following structural formula:
Figure FDA0002415296280000011
asterisks in the above structural formula indicate repeating units.
2. The quantum dot-coated carbazolyl conjugated microporous polymer microspheres according to claim 1, wherein the diameter of the quantum dot-coated carbazolyl conjugated microporous polymer microspheres is 50-750 nm.
3. The quantum dot-encapsulated carbazolyl conjugated microporous polymer microspheres according to claim 1, wherein said quantum dots are selected from green quantum dots, red quantum dots or a mixture of both.
4. The quantum dot-encapsulated carbazolyl conjugated microporous polymer microspheres according to claim 3, wherein the quantum dots consist of green quantum dots and red quantum dots.
5. The quantum dot-coated carbazolyl conjugated microporous polymer microspheres according to claim 4, wherein the weight ratio of the green quantum dots to the red quantum dots is 1: 1.
6. a method for preparing the quantum dot-encapsulated carbazolyl conjugated microporous polymer microspheres according to any one of claims 1 to 5, wherein the method comprises the following steps:
(1) adding ferric trichloride powder into an ethanol solution dissolved with sodium citrate and cadmium selenide quantum dots, then dropwise adding a chloroform solution dissolved with carbazolyl monomers, and reacting at room temperature;
(2) filtering, washing and Soxhlet extracting to obtain carbazolyl conjugated microporous polymer microspheres wrapping the quantum dots;
the carbazolyl monomer is 1, 4-di (9-carbazole) benzene; the feeding ratio of the carbazolyl monomer to the ferric chloride is 1: 0.2-20; the material ratio of the carbazolyl monomer to the cadmium selenide quantum dot is 1: 0.1 to 10; the feeding ratio of the carbazolyl monomer to the sodium citrate is 1: 0.1-10, wherein the feeding ratio refers to the weight ratio of the added raw materials.
7. The preparation method of the quantum dot-coated carbazolyl conjugated microporous polymer microspheres according to claim 6, wherein a charge ratio of the carbazolyl monomer to the cadmium selenide quantum dots is 1: 1.
8. the preparation method of the quantum dot-coated carbazolyl conjugated microporous polymer microspheres according to claim 6, wherein the charge ratio of the carbazolyl monomer to the sodium citrate is 1: 1.
9. a quantum dot film, comprising a quantum dot glue layer, wherein the quantum dot glue layer comprises the carbazolyl conjugated microporous polymer microspheres wrapping quantum dots as claimed in any one of claims 1 to 5.
10. Use of the quantum dot film of claim 9, wherein the quantum dot film is used in a liquid crystal display module.
CN201810095335.4A 2018-01-31 2018-01-31 Quantum dot-coated carbazolyl conjugated microporous polymer microsphere and preparation method thereof, quantum dot film and application thereof Active CN108384530B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810095335.4A CN108384530B (en) 2018-01-31 2018-01-31 Quantum dot-coated carbazolyl conjugated microporous polymer microsphere and preparation method thereof, quantum dot film and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810095335.4A CN108384530B (en) 2018-01-31 2018-01-31 Quantum dot-coated carbazolyl conjugated microporous polymer microsphere and preparation method thereof, quantum dot film and application thereof

Publications (2)

Publication Number Publication Date
CN108384530A CN108384530A (en) 2018-08-10
CN108384530B true CN108384530B (en) 2020-06-16

Family

ID=63074258

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810095335.4A Active CN108384530B (en) 2018-01-31 2018-01-31 Quantum dot-coated carbazolyl conjugated microporous polymer microsphere and preparation method thereof, quantum dot film and application thereof

Country Status (1)

Country Link
CN (1) CN108384530B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI693455B (en) 2019-04-10 2020-05-11 瑞軒科技股份有限公司 Led backlight module
CN111933667B (en) * 2020-08-12 2023-09-05 京东方科技集团股份有限公司 Display panel, manufacturing method thereof and display device

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106898492A (en) * 2017-01-16 2017-06-27 华南师范大学 A kind of preparation method and applications for being conjugated microporous polymer film
CN107459657A (en) * 2017-07-27 2017-12-12 苏州大学 Conjugation microporous polymer and its application containing part
CN107629197A (en) * 2017-09-30 2018-01-26 华南协同创新研究院 Blue light frequency-doubling luminescent material and its preparation method and application based on naphtho- indenes carbazole unit

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106898492A (en) * 2017-01-16 2017-06-27 华南师范大学 A kind of preparation method and applications for being conjugated microporous polymer film
CN107459657A (en) * 2017-07-27 2017-12-12 苏州大学 Conjugation microporous polymer and its application containing part
CN107629197A (en) * 2017-09-30 2018-01-26 华南协同创新研究院 Blue light frequency-doubling luminescent material and its preparation method and application based on naphtho- indenes carbazole unit

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Quantum-Dot and Polychalcone Mixed Nanocomposites for Polymer Light-Emitting Diodes";VanarajRamkumar et al.，;《Hindawi Journal of Nanomaterials》;20171023;第1-8页 *

Also Published As

Publication number Publication date
CN108384530A (en) 2018-08-10

Similar Documents

Publication Publication Date Title
JP6332522B1 (en) Composition and method for producing the composition
KR101879016B1 (en) Self emission type photosensitive resin composition, color filter manufactured using thereof and image display device having the same
KR101811103B1 (en) Self emission type photosensitive resin composition, color filter using thereof and image display device having the same
TWI766999B (en) Film
US11807786B2 (en) Quantum dot dispersed resin molded body, quantum dot dispersed colloid, and light emitting device
US20160289552A1 (en) Quantum Dots Stabilized With A Metal Thiol Polymer
CN108384530B (en) Quantum dot-coated carbazolyl conjugated microporous polymer microsphere and preparation method thereof, quantum dot film and application thereof
EP4072992A1 (en) Composition
TW201910446A (en) Ink composition, film, and display
CN107828416A (en) A kind of quantum dot fluorescence composite and its preparation method and application
CN108484906B (en) Fluorenyl conjugated microporous polymer diffusion particle with quantum dots complexed and preparation method thereof, quantum dot diffusion film and application thereof
CN110551304A (en) Cesium-lead halogen inorganic perovskite quantum dot/transparent polymer composite film
JP2017512237A (en) Method for producing quantum dot polymer film
JP2019537064A (en) Self-luminous photosensitive resin composition, color filter and image display device manufactured using the same
CN110511739A (en) A kind of preparation method of acrylic polymer coated quantum dots
CN113943410B (en) Quantum dot film, preparation method thereof and quantum dot light-emitting diode
TW201936889A (en) Composition, film, laminate structure, light emitting device and display
CN109762555B (en) Quantum dot glue composition, quantum dot film and preparation method thereof
JP2022527600A (en) Composition
CN105694042B (en) Light diffusion powder, preparation method of light diffusion powder, quantum dot photoresist and quantum dot color film
CN108373534B (en) Quantum dot-loaded conjugated microporous polymer and preparation method thereof, quantum dot membrane and liquid crystal display module
CN108169840B (en) Light guide plate, preparation method thereof and liquid crystal display module
WO2019233201A1 (en) Yellow-red band quantum dots, synthesis method therefor and application thereof
Fan et al. Near-infrared luminescent copolymerized hybrid materials built from tin nanoclusters and PMMA
WO2022032811A1 (en) Barium-titanium complex and preparation method therefor, and display panel

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