CN111077713A - Optically addressable optically erasable fluorescent/reflective dual-mode transparent display device - Google Patents

Optically addressable optically erasable fluorescent/reflective dual-mode transparent display device Download PDF

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CN111077713A
CN111077713A CN201811223060.4A CN201811223060A CN111077713A CN 111077713 A CN111077713 A CN 111077713A CN 201811223060 A CN201811223060 A CN 201811223060A CN 111077713 A CN111077713 A CN 111077713A
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compound
organic solvent
display device
contact reaction
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CN111077713B (en
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郭金宝
李俊涛
林思阳
隽奥
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Beijing University of Chemical Technology
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    • 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
    • G02F1/137—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 characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering
    • G02F1/13718—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 characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering based on a change of the texture state of a cholesteric liquid crystal
    • 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 
    • G02F1/0126—Opto-optical modulation, i.e. control of one light beam by another light beam, not otherwise provided for in this subclass
    • 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
    • G02F1/1313—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 specially adapted for a particular application

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Abstract

The invention discloses a fluorescent/reflective dual-mode transparent display device capable of being erased by light addressable, which comprises: the liquid crystal display panel comprises a cholesteric liquid crystal composition layer, a polymer wall layer, a first transparent substrate and a second transparent substrate; and a polymer wall layer is arranged between the first transparent substrate and the second transparent substrate, and cholesteric liquid crystals are arranged in the polymer wall layer. The liquid crystal dopant molecule with the photo-reversible isomerism, the fluorescence and the chirality simultaneously is prepared, so that the transparent display prepared by the molecules has excellent photo-response performance, the fluorescence with different colors and different intensities can be obtained on the liquid crystal display only through light control, the process can be repeatedly carried out by switching the irradiation with different wavelengths, and the display device can be repeatedly utilized.

Description

Optically addressable optically erasable fluorescent/reflective dual-mode transparent display device
Technical Field
The invention belongs to the technical field of liquid crystal display devices, and particularly relates to a fluorescent/reflective dual-mode transparent display device capable of being erased by light addressable light.
Background
Cholesteric liquid crystals can selectively reflect visible light due to their unique helical structure, and the selective reflection follows the bragg formula: λ is n × p, where λ is the central wavelength of the cholesteric liquid crystal selective reflection light, n is the average refractive index of the liquid crystal host material, and p is the helical pitch of the cholesteric liquid crystal. The color of the reflected light can be adjusted by adjusting the size of the screw pitch. The cholesteric liquid crystal display prepared according to the principle does not need a backlight screen and has the characteristics of low energy consumption, eye protection and the like. In order to further simplify the display structure, complicated driving circuits are omitted, and cholesteric liquid crystals can be made using liquid crystal materials having a photoresponse. Meanwhile, because the cholesteric liquid crystal display has the defects of insufficient contrast and difficulty in image resolution in a dark environment, a fluorescent substance is introduced into the cholesteric liquid crystal display at present, so that the display can generate a fluorescent pattern with high contrast only by weak exciting light in the dark, and the defects of the cholesteric liquid crystal display are greatly overcome. In the existing system, a fluorescent agent is mainly added into cholesteric liquid crystal, and the system usually needs to apply an extra electric field or change other external conditions to regulate and control the fluorescence intensity of a specific position on a display, so that the assembly of a liquid crystal display device is complicated, and the cost is increased; the patent application with publication number CN201611044019.1 mentions a fluorescent chiral molecule with light response, and a cholesteric liquid crystal display using the molecule as a dopant can adjust the reflection color and fluorescence intensity by illumination without an additional driving circuit, but the adjustment is irreversible and cannot be reused, resulting in waste. In view of the above, there is a need to develop a fluorescent cholesteric liquid crystal display device capable of performing backlight modulation, so as to greatly improve the practicability of the cholesteric liquid crystal display device and reduce the use cost thereof.
Disclosure of Invention
The invention aims to provide a flexible fluorescent cholesteric liquid crystal display device which can carry out reversible light regulation and control and can write information remotely through laser. Writing a text pattern directly on the display device by using 365nm laser irradiation; the written information can be erased by the irradiation of blue light with 450nm, and can be repeatedly erased and written.
To achieve the above object, the present invention provides an optically addressable optically erasable dual mode fluorescent/reflective transparent display device, comprising: the liquid crystal display panel comprises a cholesteric liquid crystal composition layer, a polymer wall layer, a first transparent substrate and a second transparent substrate; and a polymer wall layer is arranged between the first transparent substrate and the second transparent substrate, and cholesteric liquid crystals are arranged in the polymer wall layer.
The technical scheme of the invention has the following beneficial effects:
(1) the liquid crystal dopant molecule with the photo-reversible isomerism, the fluorescence and the chirality simultaneously is prepared, so that the transparent display prepared by the molecules has excellent photo-response performance, the fluorescence with different colors and different intensities can be obtained on the liquid crystal display only through light control, the process can be repeatedly carried out by switching the irradiation with different wavelengths, and the display device can be repeatedly utilized.
(2) The display device can write information remotely through 365nm laser, can be directly written by hands or can be written by a precision instrument in a programming way, and is convenient and various to operate.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
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The above and other objects, features and advantages of the present invention will become more apparent by describing in more detail exemplary embodiments thereof with reference to the attached drawings, in which like reference numerals generally represent like parts throughout.
FIG. 1 shows a simplified structural diagram of an optically addressable optically erasable fluorescent/reflective dual mode transparent display device, according to one embodiment of the present invention. In the figure, black circles represent chiral fluorescent molecules having a reversible photoresponse, and black lines represent cholesteric liquid crystals.
Fig. 2 shows a schematic diagram of an optically addressable optically erasable fluorescent/reflective dual mode transparent display device according to an embodiment of the present invention showing different colors and different intensities of fluorescence under different lighting conditions.
FIG. 3 illustrates a reflection spectrum of a photo-addressable, photo-erasable fluorescent/reflective dual-mode transparent display device in different illuminations according to one embodiment of the present invention.
FIG. 4 shows a fluorescence spectrum of an optically addressable optically erasable fluorescent/reflective dual mode transparent display device under different illumination according to one embodiment of the present invention.
Fig. 5 shows a schematic diagram of the effect of an optically addressable optically erasable fluorescent/reflective dual mode transparent display device according to an embodiment of the present invention in actual use.
Fig. 6 is a graph showing the effect of example 1 of the present invention compared with that of comparative example 1 after 24 hours of information writing.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
The invention provides an optically addressable optically erasable dual mode transparent display device, comprising: the liquid crystal display panel comprises a cholesteric liquid crystal composition layer, a polymer wall layer, a first transparent substrate and a second transparent substrate; and a polymer wall layer is arranged between the first transparent substrate and the second transparent substrate, and cholesteric liquid crystals are arranged in the polymer wall layer.
The fluorescence/reflection dual-mode transparent display device capable of being erased by the light addressable light has the advantages that when the device is irradiated by using 450nm blue light, the reflected light color is red-shifted, the fluorescence intensity is reduced, and after the device is irradiated by using 365nm ultraviolet light, the reflected light color is blue-shifted, the fluorescence intensity is increased, and the operation and the change can be repeated for many times. Meanwhile, the reflection band can be in a near infrared region through illumination, and at the moment, no visible light color is reflected, so that the film is in a colorless transparent state.
In the invention, the surface of the polymer wall layer contains a plurality of adjacent grids, and the cholesteric liquid crystal is limited in each grid so as to increase the stability of storing the optical writing information.
Preferably, the first transparent substrate and the second transparent substrate are made of the same material and are at least one of polypropylene, polystyrene, polycarbonate, polymethyl methacrylate, polyethylene terephthalate and transparent nylon.
According to the present invention, preferably, the cholesteric liquid crystal composition layer includes 0.1 to 15 wt% of chiral fluorescent molecules having reversible photoresponse and 85 to 99.9 wt% of nematic liquid crystal, based on the total weight of the cholesteric liquid crystal composition layer.
Preferably, the preparation method of the cholesteric liquid crystal composition comprises the following steps: in the presence of an organic solvent, uniformly mixing chiral fluorescent molecules with reversible photoresponse and nematic liquid crystal, and evaporating the solvent to obtain the cholesteric liquid crystal composition. Wherein the organic solvent is at least one of acetone, methanol, ethanol, tetrahydrofuran, dichloromethane and chloroform.
The invention utilizes the selective reflection characteristic of cholesteric liquid crystal, induces the chiral fluorescent molecular switch to isomerize by using the illumination with different wavelengths, thereby changing the pitch P of the cholesteric liquid crystal through small disturbance, and leading the liquid crystal to reflect different colors and display fluorescence with different intensities. Information is directly written on the display through ultraviolet laser irradiation (wherein, the part irradiated by the laser reflects red light, shows red color and has high-brightness yellow fluorescence, the part not irradiated by the laser reflects near infrared light, shows colorless transparency and has weak yellow fluorescence), the position irradiated by the laser is controlled through a manual control or a precise instrument, a desired pattern or character can be conveniently or precisely written, and the pattern or character can show high contrast under the condition of white light illumination or weak excitation light illumination in the dark. The written information can be erased by applying 450nm blue light irradiation to the device, and then repeated writing/erasing can be carried out by using 365nm/450nm light, so that the display device can be reused.
According to the invention, preferably, the chiral fluorescent molecule with reversible photoresponse is shown as a general formula I, M1Selected from the group of formula II, formula III or formula IV, M2Selected from the group consisting of those of formula V or formula VI, wherein R1、R2、R3、R4Same or different, each independently selected from hydrogen atom, C1-C6Alkyl or C1-C5N is an integer of 1 to 6.
Figure BDA0001835272950000051
The chiral fluorescent molecule with reversible photoresponse can perform a light isomerization reaction shown as a formula 1 under the irradiation of blue light with the wavelength of 450nm, and two light isomerization changes occur; under the irradiation of ultraviolet light with the wavelength of 365nm, the photo-isomerism reversible change can be generated.
Figure BDA0001835272950000052
According to the invention, preferably, the chiral fluorescent molecule with reversible photoresponsiveness is at least one of chiral compounds with structures shown in general formulas a-1, a-2, b-1 and b-2; wherein R is1、R2、R3、R4Same or different, each independently selected from hydrogen atom, C1-C6Alkyl or C1-C5X is an oxygen atom or a sulfur atom, and n is an integer of 1 to 6.
Figure BDA0001835272950000061
According to the present invention, preferably, the method for preparing the chiral fluorescent molecule having reversible photoresponsiveness is selected from the first preparation method or the second preparation method;
wherein the first preparation method comprises the following steps:
(1) in the presence of a first organic solvent, carrying out contact reaction on a compound I and pivaloyl chloride to obtain a compound II;
(2) in the presence of a first organic solvent, carrying out contact reaction on the compound II and liquid bromine to obtain a compound III;
(3) carrying out contact reaction on the compound III and methanol in the presence of a second organic solvent and a first alkaline regulator to obtain a mixture; in the presence of a third organic solvent and a second basic regulator, carrying out contact reaction on the mixture and a compound IV to obtain a compound V;
(4) in the presence of a fourth organic solvent, a first catalyst and a second catalyst, carrying out contact reaction on the compound V and sodium acetonitrile acetate to obtain a compound VI;
(5) in the presence of a fifth organic solvent and a third alkaline regulator, carrying out contact reaction on 2, 5-thiophenedicarboxaldehyde, 2, 5-furandicarbaldehyde or a compound X and the compound VI to obtain the chiral fluorescent molecule with the reversible photoresponse;
the second preparation method comprises the following steps:
(1) in the presence of a third organic solvent and a second basic regulator, carrying out contact reaction on the compound I and a compound IV to obtain a compound VII;
(2) in the presence of a sixth organic solvent, carrying out contact reaction on the compound VII, n-butyllithium and dibromotetrachloroethane to obtain a compound VIII;
(3) in the presence of a fourth organic solvent, a first catalyst and a second catalyst, carrying out contact reaction on the compound VII and sodium acetonitrile acetate to obtain a compound IX;
(4) in the presence of a fifth organic solvent and a third alkaline regulator, carrying out contact reaction on 2, 5-thiophenedicarboxaldehyde, 2, 5-furandicarbaldehyde or a compound X and the compound IX to obtain the chiral fluorescent molecule with the reversible photoresponse;
wherein the structural formula of the compound I is as follows:
Figure BDA0001835272950000081
the structural formula of the compound II is as follows:
Figure BDA0001835272950000082
the structural formula of the compound III is as follows:
Figure BDA0001835272950000083
the structural formula of the compound IV is as follows:
Figure BDA0001835272950000084
wherein X is selected from bromine atom or iodine atom, and n is an integer of 1-6;
the structural formula of the compound V is as follows:
Figure BDA0001835272950000085
wherein n is an integer of 1 to 6;
the structural formula of the compound VI is as follows:
Figure BDA0001835272950000086
wherein n is an integer of 1 to 6;
the structural formula of the compound VII is as follows:
Figure BDA0001835272950000091
wherein n is an integer of 1 to 6;
the structural formula of the compound VIII is as follows:
Figure BDA0001835272950000092
wherein n is an integer of 1 to 6;
the structural formula of the compound IX is as follows:
Figure BDA0001835272950000093
wherein n is an integer of 1 to 6;
the compound X has the structural formula:
Figure BDA0001835272950000094
in the formula, R1、R2、R3、R4Same or different, each independently selected from hydrogen atom, C1-C6Alkyl or C1-C5Alkoxy group of (2).
According to the present invention, it is preferable that,
the reaction conditions of the steps in the first preparation method include the following:
in the step (1), the first organic solvent is dichloromethane, the contact reaction temperature is 0-30 ℃, and the contact reaction time is 1-3 h; the molar ratio of the compound I to the pivaloyl chloride is 0.5-2: 1;
in the step (2), the contact reaction temperature is 0-30 ℃ and the time is 1-3 h; the molar ratio of the compound II to the liquid bromine is 0.5-2: 1;
in the step (3), the second organic solvent is methanol, the third organic solvent is acetone, the first alkaline regulator is potassium hydroxide, and the second alkaline regulator is anhydrous potassium carbonate; the molar ratio of the compound III to the potassium hydroxide to the compound IV to the anhydrous potassium carbonate is 1-10: 1: 1-10: 2-20 ℃, wherein the reaction temperature of the compound III and methanol is 0-50 ℃, and the reaction time is 1-3 h; the reaction temperature of the mixture and the compound IV is 0-70 ℃, and the reaction time is 10-15 h;
in the step (4), the fourth organic solvent is anhydrous xylene; the first catalyst is allylpalladium (II) chloride dimer; the second catalyst is 2-dicyclohexylphosphine-2 ',6' -dimethoxybiphenyl; the molar ratio of the first catalyst to the second catalyst to the compound V to the sodium acetonitrile acetate is 0.01-0.03: 0.03-0.1: 0.25-1: 1; the contact reaction temperature is 100-150 ℃, and the time is 10-15 h;
in the step (5), the fifth organic solvent is tetrahydrofuran, the second basic regulator is potassium tert-butoxide, and the molar ratios of the 2, 5-thiophenedicarboxaldehyde, the 2, 5-furandicarbaldehyde or the compound X to the compound VI are all 0.4-0.6: 1; the molar ratio of the compound VI to the potassium tert-butoxide is 1: 0.1 to 1; the contact reaction temperature is 0-50 ℃ and the time is 6-24 h;
the reaction conditions of the steps in the second preparation method include the following:
in the step (1), the third organic solvent is acetone; the contact reaction temperature is 40-60 ℃ and the time is 20-30 h; the molar ratio of the compound I to the anhydrous potassium carbonate to the compound IV is 1:5-10: 1-2;
in the step (2), the sixth organic solvent is anhydrous tetrahydrofuran, the contact reaction temperature is-65 to-75 ℃, and the contact reaction time is 2 to 4 hours; the molar ratio of the compound VII, n-butyl lithium to dibromotetrachloroethane is 1:1-1.5: 1-3;
in the step (3), the fourth organic solvent is anhydrous xylene; the first catalyst is allylpalladium (II) chloride dimer; the second catalyst is 2-dicyclohexylphosphine-2 ',6' -dimethoxybiphenyl; the molar ratio of the first catalyst to the second catalyst to the compound VIII to the sodium acetonitrile acetate is 0.01-0.03: 0.03-0.1: 0.25-1: 1; the contact reaction temperature is 100-150 ℃, and the time is 10-15 h;
in the step (4), the fifth organic solvent is tetrahydrofuran, the third basic regulator is potassium tert-butoxide, and the molar ratio of the 2, 5-thiophenedicarboxaldehyde, the 2, 5-furandicarbaldehyde or the compound x to the compound ix is 0.4 to 0.6: 1; the molar ratio of the compound IX to potassium tert-butoxide is 1: 0.1 to 1; the contact reaction temperature is 0-50 ℃, and the reaction time is 6-24 h.
According to the present invention, preferably, said nematic liquid crystal is selected from at least one of slc1717, E7, E44, E48, slc7011 and slc 1011.
According to the present invention, preferably, the polymer wall layer is prepared by the following method: and coating a mixture comprising an acrylate prepolymer, a photosensitive monomer and a photoinitiator on a transparent substrate, preheating, selectively exposing by ultraviolet, and finally washing an unpolymerized area by a developing solution to obtain the polymer wall layer.
In the invention, the acrylate prepolymer, the photosensitive monomer and the photoinitiator are mixed under the condition of keeping out of the sun.
In the present invention, it is preferable to selectively cover the mixture coated on the transparent substrate with a mask; through ultraviolet exposure, as the light-transmitting area of the mask is in a grid shape, the exposed area of the mixture can also form the same grid-shaped polymer; wherein the shape of the mask light-transmitting area comprises but is not limited to one or more of a grid shape, a regular hexagon honeycomb shape and a triangle shape; the mixture covered by the shaded area of the mask does not undergo a crosslinking reaction.
In the present invention, the developing solution is preferably a weakly alkaline salt solution.
According to the present invention, preferably, the photosensitive monomer is at least one of a monofunctional acrylate photosensitive monomer, a difunctional acrylate photosensitive monomer and a trifunctional acrylate photosensitive monomer;
the monofunctional acrylate photosensitive monomer is isobornyl acrylate and/or 2-phenoxyethyl acrylate, the difunctional acrylate photosensitive monomer is 1, 6-hexanediol diacrylate and/or ethoxy bisphenol A dimethacrylate, and the trifunctional acrylate photosensitive monomer is ethoxy trimethylolpropane triacrylate;
the photoinitiator is α' -dimethylbenzyl ketal;
the mixing temperature of the mixture is 60-90 ℃; the preheating temperature is 60-90 ℃, and the preheating time is 1-2 h.
According to the present invention, preferably, the first transparent substrate and the second transparent substrate are both transparent substrates subjected to an antiparallel process.
In the present invention, the use of the transparent substrate processed in an antiparallel manner contributes to better photoresponse.
In the present invention, the light source used for writing/erasing information includes, but is not limited to, one or more of a point light source, a surface light source, and a laser light source.
The invention is further illustrated by the following examples:
1. preparation of chiral fluorescent molecules with reversible photoresponse:
preparation example 1
(1) 2.8g of the compound I, 2.67g of diiodomethane and 2.0g of anhydrous potassium carbonate are mixed and added into 50ml of acetone, and stirred for 24 hours at 50 ℃ to obtain 2,2 '-methylenedioxy-1, 1' -binaphthyl;
(2) mixing 1g of 2,2 '-methylenedioxy-1, 1' -binaphthyl and n-butyllithium at a molar ratio of 1:1 in anhydrous tetrahydrofuran at-70 ℃, adding 3g of dibromotetrachloroethane, stirring for 3 hours, evaporating the solvent, and purifying by column chromatography to obtain 3-bromo-2, 2 '-methylenedioxy-1, 1' -binaphthyl;
(3) 1g of 3-bromo-2, 2 '-methylenedioxy-1, 1' -binaphthyl was mixed with 0.5g of sodium acetonitrile acetate, 0.02g of allylpalladium (II) chloride dimer, 0.06g of 2-dicyclohexylphosphine-2 ',6' -dimethoxybiphenyl in anhydrous xylene, heated to 130 ℃ and stirred for 12 hours, and the solvent was evaporated and purified by column chromatography to give 3-acetonitrile-2, 2 '-methylenedioxy-1, 1' -binaphthyl.
(4) In 5ml of tetrahydrofuran, 0.16g of 3-acetonitrile-2, 2 '-methylenedioxy-1, 1' -binaphthyl, 0.04g of 1, 4-terephthalaldehyde and 0.01g of potassium tert-butoxide were mixed, reacted at room temperature for 24 hours, and after evaporation of the solvent, the mixture was purified by column chromatography to obtain compound 1 (see Table 1).
Preparation example 2
(1) In dichloromethane, 2.8g of binaphthol and 1.2g of pivaloyl chloride are mixed, and stirred and reacted for 2 hours at the temperature of 25 ℃ to obtain a compound II;
(2) mixing 3.0g of compound II and 1.6g of liquid bromine in dichloromethane, and stirring at 25 ℃ for reacting for 2 hours to obtain a compound III;
(3) mixing 3.0g of compound III and 0.5g of potassium hydroxide in 50mL of methanol, stirring the mixture at 25 ℃ for reaction for one hour, then spin-drying the solvent, mixing the obtained mixture with 2.5g of diiodomethane and 10g of anhydrous potassium carbonate, heating the mixture in acetone to 50 ℃, stirring the mixture for reaction for 12 hours, and purifying the mixture by column chromatography to obtain 6-bromo-2, 2 '-methylenedioxy-1, 1' -binaphthyl;
(4) 1g of 6-bromo-2, 2 '-methylenedioxy-1, 1' -binaphthyl was mixed with 0.5g of sodium acetonitrile acetate, 0.02g of allylpalladium (II) chloride dimer, 0.06g of 2-dicyclohexylphosphine-2 ',6' -dimethoxybiphenyl in anhydrous xylene, heated to 130 ℃ and stirred for 12 hours to obtain 6-acetonitrile-2, 2 '-methylenedioxy-1, 1' -binaphthyl by purification by column chromatography.
(5) In 5ml of tetrahydrofuran, 0.16g of 6-acetonitrile-2, 2 '-methylenedioxy-1, 1' -binaphthyl, 0.04g of 1, 4-terephthalaldehyde and 0.01g of potassium tert-butoxide were mixed, reacted at room temperature for 24 hours, and after evaporation of the solvent, the mixture was purified by column chromatography to obtain compound 2 (see Table 1).
Preparation example 3
0.16g of 3-acetonitrile-2, 2 '-methylenedioxy-1, 1' -binaphthyl obtained in step (3) of production example 1, 0.04g of 2, 5-thiophenedicarboxaldehyde and 0.01g of potassium tert-butoxide were mixed in 5ml of tetrahydrofuran, reacted at room temperature for 24 hours, and then the solvent was distilled off and purified by column chromatography to obtain compound 3 (see Table 1).
Preparation example 4
In 5ml of tetrahydrofuran, 0.16g of 6-acetonitrile-2, 2 '-methylenedioxy-1, 1' -binaphthyl obtained in the step (4) of preparation example 2, 0.04g of 2, 5-thiophenedicarboxaldehyde and 0.01g of potassium tert-butoxide were mixed and reacted at room temperature for 24 hours, and after evaporation of the solvent, purification was performed by column chromatography to obtain compound 4 (see Table 1).
TABLE 1 structures of Compound 1, Compound 2, Compound 3 and Compound 4 and their Hydrogen spectra data
Figure BDA0001835272950000131
Figure BDA0001835272950000141
2. Preparation of polymer wall layer
Preparation example 5
2g of an acrylate prepolymer, 1g of isobornyl acrylate, 0.5g of 1, 6-hexanediol diacrylate, 0.5g of ethoxytrimethylolpropane triacrylate, and 0.16g of α' -dimethylbenzylketal were weighed, and the mixture was driedMixing the materials, and stirring thoroughly in dark to obtain mixture; uniformly coating the mixture on a PET plate in a roller coating mode; placing the PET plate on a horizontal electric heating plate at 80 deg.C, standing in dark for 2h, taking off, applying a mask thereon at 4.5mW/cm2Is exposed for 10 s.
Weighing 6g of anhydrous sodium carbonate, adding the anhydrous sodium carbonate into 1.494kg of deionized water, uniformly mixing to prepare a sodium carbonate aqueous solution with the mass fraction of 0.4%, pressurizing and washing the exposed PET plate by using the sodium carbonate solution, and washing off the non-crosslinked mixture in the unexposed area to obtain the crosslinked polymer in the exposed area, namely the polymer wall layer.
Preparation example 6
Weighing 2g of acrylate prepolymer, 1g of 2-phenoxyethyl acrylate, 1g of ethoxy bisphenol A dimethacrylate, 0.25g of ethoxy trimethylolpropane triacrylate and 0.16g of α' -dimethylbenzyl ketal, mixing the above materials, sufficiently stirring the mixture in dark to obtain a mixture, uniformly coating the mixture on a PET plate in a roller coating manner, placing the PET plate on a horizontal electric heating plate at 80 ℃, placing the PET plate in dark for 2 hours, taking the PET plate off, applying a mask on the PET plate, and keeping the thickness of the mask at 4.5mW/cm2Is exposed for 10 s.
Weighing 6g of anhydrous sodium carbonate, adding the anhydrous sodium carbonate into 1.494kg of deionized water, uniformly mixing to prepare a sodium carbonate aqueous solution with the mass fraction of 0.4%, pressurizing and washing the exposed PET plate by using the sodium carbonate solution, and washing off the non-crosslinked mixture in the unexposed area to obtain the crosslinked polymer in the exposed area, namely the polymer wall layer.
3. Preparation of optically addressable optically erasable fluorescent/reflective dual-mode transparent display device
Example 1
SLC-1717 from honest-Yonghua display materials, Inc. was used as a nematic liquid crystal and was mixed with chiral fluorescent molecules having a reversible photoresponse, represented by compound 2 in table 1, in methylene chloride to obtain the cholesteric liquid crystal composition (86.2 wt% nematic liquid crystal and 13.8 wt% compound 2, based on the total weight of the cholesteric liquid crystal composition), which was then uniformly coated on the PET sheet having the polymer wall layer (prepared in preparation example 5), and then covered with another PET sheet and the frame around the device was encapsulated to prepare a photo-addressable, photo-erasable, dual-mode fluorescent/reflective transparent display device (see fig. 1).
Comparative example 1
In dichloromethane, selecting SLC-1717 from Chengzhitong display materials GmbH as nematic liquid crystal, mixing with chiral fluorescent molecules with reversible photoresponse shown as compound 2 in Table 1 to obtain the cholesteric liquid crystal composition (based on the total weight of the cholesteric liquid crystal composition, the content of nematic liquid crystal is 86.2 wt%, and the content of compound 2 is 13.8 wt%), adding 6 μm polystyrene spacer balls accounting for 1% of the total weight of the cholesteric liquid crystal composition into the cholesteric liquid crystal composition, injecting a system formed by the cholesteric liquid crystal composition and the spacer balls between two PET plates, and then packaging the frame around the device to obtain the cholesteric liquid crystal display device.
Comparative example 2
In dichloromethane, SLC-1717 selected from Chengzhitong display materials GmbH is used as nematic liquid crystal and is mixed with photoresponse chiral fluorescent molecular compound a (the structural formula is shown as below) to obtain the cholesteric liquid crystal composition (the content of nematic liquid crystal is 95 wt% and the content of compound a is 5 wt% based on the total weight of the cholesteric liquid crystal composition), the cholesteric liquid crystal composition is uniformly coated on the PET plate containing the polymer wall layer (prepared by preparation example 5), then the PET plate is covered with another PET plate, and the frame around the device is packaged to obtain the cholesteric liquid crystal display device.
Wherein the molecular structural formula of the compound a is as follows:
test example 1
The photo-addressable, photo-erasable, dual-mode, fluorescent/reflective transparent display device prepared in example 1 was illuminated with blue light and a 365nm laser, respectively, and the writing and erasing of information was observed.
As shown in fig. 2 to 4, the photo-addressable dual-mode fluorescence/reflectance transparent display device with photo-erasability prepared in example 1 initially has a central reflectance wavelength of 450nm and a central wavelength of a fluorescence emission peak under irradiation of blue light at 450nm of 535 nm; the wavelength is 450nm, and the intensity is 20mW/cm2When the blue light is irradiated for 2min at room temperature, the central reflection wavelength of the display is red-shifted to 780nm, and the display is colorless and transparent at the moment, and the yellow fluorescence emitted by the display under the excitation of the blue light is weaker in intensity and can be regarded as information erasure; irradiating the display for 2s at room temperature by using laser with the wavelength of 365nm and the intensity of 5MW, wherein the central reflection wavelength of the part of the display irradiated by the laser is blue-shifted to 675nm, and at the moment, the display shows red, and yellow fluorescence emitted by the display under the excitation of the blue light has stronger intensity and can be regarded as information writing; then the wavelength is 450nm, and the intensity is 20mW/cm2After the blue light is irradiated for 2min at room temperature, the central reflection wavelength of the display is re-red shifted to 780nm, which shows that the display can be repeatedly written and erased for many times. The display device has good contrast, can display red or yellow fluorescence simultaneously, and can write text patterns and symbols remotely by using a handheld laser, as shown in fig. 5, which is very convenient; the written pattern was clearly resolved after 24 hours of storage in the dark.
Test example 2
The cholesteric liquid crystal display device prepared in comparative example 1 was irradiated with blue light and laser light having a wavelength of 365nm, respectively, and the writing and erasing of information thereof were observed.
Similar to the results of test example 1, a wavelength of 450nm and an intensity of 20mW/cm were used2The blue light is irradiated for 2min at room temperature, so that the central reflection wavelength of the display device is red-shifted from 450nm to 780nm, the display device is colorless, and the fluorescence intensity is greatly reduced; then 365nm laser is used for irradiation, the central reflection wavelength of the irradiated area is blue-shifted from 780nm to 675nm, at the moment, red is displayed, and the yellow fluorescence intensity emitted by the laser under the excitation of blue light is enhanced; then the wavelength is 450nm, and the intensity is 20mW/cm2After the blue light is irradiated for 2min at room temperature, the central reflection wavelength of the display device is re-red shifted to 780nm, which shows that the display device can be repeatedly written and erased for many times. As shown in the figure6, except that the pattern written with the 365nm laser was blurred due to the thermal movement of the molecules after being stored in the dark for 24 hours, and the writing was difficult to recognize. The pattern in the display device prepared in example 1 was still clearly visible, which shows that the cholesteric liquid crystal display device having the polymer wall can improve the information storage effect by comparison.
Test example 3
The cholesteric liquid crystal display device prepared in comparative example 2 was irradiated with blue light and laser light having a wavelength of 365nm, respectively, and the writing and erasing of information thereof were observed.
The cholesteric liquid crystal display device prepared in comparative example 2 initially had a central reflection wavelength of 450nm and a fluorescence emission peak having a central wavelength of 520 nm; the wavelength is 450nm, and the intensity is 20mW/cm2When the blue light is irradiated for 2min at room temperature, the display device has no obvious change, which shows that the display device is not sensitive to visible light and cannot be erased and written by using visible light; irradiating for two seconds by using 365nm laser, wherein the central reflection spectrum of the irradiated area is shifted to 652nm, the irradiated area is red, the fluorescence intensity is greatly reduced, and the irradiated area can be regarded as information writing; irradiating the fluorescent material by using visible light or ultraviolet light, wherein the blue shift of the central reflection spectrum of the irradiated area cannot be realized, and the fluorescence intensity cannot be recovered; indicating that the cholesteric liquid crystal display device does not have reversible photo-erase performance.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.

Claims (10)

1. An optically addressable optically erasable dual mode fluorescent/reflective transparent display device, the transparent display device comprising: the liquid crystal display panel comprises a cholesteric liquid crystal composition layer, a polymer wall layer, a first transparent substrate and a second transparent substrate; and a polymer wall layer is arranged between the first transparent substrate and the second transparent substrate, and cholesteric liquid crystals are arranged in the polymer wall layer.
2. An optically addressable optically erasable fluorescent/reflective dual mode transparent display device according to claim 1, wherein said cholesteric liquid crystal composition layer comprises 0.1-15 wt% chiral fluorescent molecules having reversible photoresponsiveness and 85-99.9 wt% nematic liquid crystal, based on the total weight of said cholesteric liquid crystal composition layer.
3. An optically addressable optically erasable dual mode fluorescent/reflective transparent display device as claimed in claim 2 wherein said chiral fluorescent molecule having reversible optical responsivity is of formula I, M1Selected from the group of formula II, formula III or formula IV, M2Selected from the group consisting of those of formula V or formula VI, wherein R1、R2、R3、R4Same or different, each independently selected from hydrogen atom, C1-C6Alkyl or C1-C5N is an integer of 1 to 6.
Figure FDA0001835272940000011
4. An optically addressable dual mode fluorescent/reflective transparent display device according to claim 3, wherein the chiral fluorescent molecules having reversible photoresponsiveness are at least one of chiral compounds of the structures represented by formula a-1, formula a-2, formula b-1 and formula b-2; wherein R is1、R2、R3、R4Same or different, each independently selected from hydrogen atom, C1-C6Alkyl or C1-C5X is an oxygen atom or a sulfur atom, and n is an integer of 1 to 6.
Figure FDA0001835272940000021
Figure FDA0001835272940000031
5. An optically addressable optically erasable fluorescent/reflective dual mode transparent display device according to claim 3 or 4, wherein the chiral fluorescent molecule having reversible optical responsivity is fabricated by a method selected from the first fabrication method or the second fabrication method;
wherein the first preparation method comprises the following steps:
(1) in the presence of a first organic solvent, carrying out contact reaction on a compound I and pivaloyl chloride to obtain a compound II;
(2) in the presence of a first organic solvent, carrying out contact reaction on the compound II and liquid bromine to obtain a compound III;
(3) carrying out contact reaction on the compound III and methanol in the presence of a second organic solvent and a first alkaline regulator to obtain a mixture; in the presence of a third organic solvent and a second basic regulator, carrying out contact reaction on the mixture and a compound IV to obtain a compound V;
(4) in the presence of a fourth organic solvent, a first catalyst and a second catalyst, carrying out contact reaction on the compound V and sodium acetonitrile acetate to obtain a compound VI;
(5) in the presence of a fifth organic solvent and a third alkaline regulator, carrying out contact reaction on 2, 5-thiophenedicarboxaldehyde, 2, 5-furandicarbaldehyde or a compound X and the compound VI to obtain the chiral fluorescent molecule with the reversible photoresponse;
the second preparation method comprises the following steps:
(1) in the presence of a third organic solvent and a second basic regulator, carrying out contact reaction on the compound I and a compound IV to obtain a compound VII;
(2) in the presence of a sixth organic solvent, carrying out contact reaction on the compound VII, n-butyllithium and dibromotetrachloroethane to obtain a compound VIII;
(3) in the presence of a fourth organic solvent, a first catalyst and a second catalyst, carrying out contact reaction on the compound VII and sodium acetonitrile acetate to obtain a compound IX;
(4) in the presence of a fifth organic solvent and a third alkaline regulator, carrying out contact reaction on 2, 5-thiophenedicarboxaldehyde, 2, 5-furandicarbaldehyde or a compound X and the compound IX to obtain the chiral fluorescent molecule with the reversible photoresponse;
wherein the structural formula of the compound I is as follows:
Figure FDA0001835272940000041
the structural formula of the compound II is as follows:
Figure FDA0001835272940000042
the structural formula of the compound III is as follows:
Figure FDA0001835272940000043
the structural formula of the compound IV is as follows:
Figure FDA0001835272940000044
wherein X is selected from bromine atom or iodine atom, and n is an integer of 1-6;
the structural formula of the compound V is as follows:
Figure FDA0001835272940000045
wherein n is an integer of 1 to 6;
the structural formula of the compound VI is as follows:
Figure FDA0001835272940000051
wherein n is an integer of 1 to 6;
the structural formula of the compound VII is as follows:
Figure FDA0001835272940000052
wherein n is an integer of 1 to 6;
the structural formula of the compound VIII is as follows:
Figure FDA0001835272940000053
wherein n is an integer of 1 to 6;
the structural formula of the compound IX is as follows:
Figure FDA0001835272940000054
wherein n is an integer of 1 to 6;
the compound X has the structural formula:
Figure FDA0001835272940000055
in the formula, R1、R2、R3、R4Same or different, each independently selected from hydrogen atom, C1-C6Alkyl or C1-C5Alkoxy group of (2).
6. An optically addressable optically erasable dual mode fluorescent/reflective transparent display device according to claim 5,
the reaction conditions of the steps in the first preparation method include the following:
in the step (1), the first organic solvent is dichloromethane, the contact reaction temperature is 0-30 ℃, and the contact reaction time is 1-3 h; the molar ratio of the compound I to the pivaloyl chloride is 0.5-2: 1;
in the step (2), the contact reaction temperature is 0-30 ℃ and the time is 1-3 h; the molar ratio of the compound II to the liquid bromine is 0.5-2: 1;
in the step (3), the second organic solvent is methanol, the third organic solvent is acetone, the first alkaline regulator is potassium hydroxide, and the second alkaline regulator is anhydrous potassium carbonate; the molar ratio of the compound III to the potassium hydroxide to the compound IV to the anhydrous potassium carbonate is 1-10: 1: 1-10: 2-20 ℃, wherein the reaction temperature of the compound III and methanol is 0-50 ℃, and the reaction time is 1-3 h; the reaction temperature of the mixture and the compound IV is 0-70 ℃, and the reaction time is 10-15 h;
in the step (4), the fourth organic solvent is anhydrous xylene; the first catalyst is allylpalladium (II) chloride dimer; the second catalyst is 2-dicyclohexylphosphine-2 ',6' -dimethoxybiphenyl; the molar ratio of the first catalyst to the second catalyst to the compound V to the sodium acetonitrile acetate is 0.01-0.03: 0.03-0.1: 0.25-1: 1; the contact reaction temperature is 100-150 ℃, and the time is 10-15 h;
in the step (5), the fifth organic solvent is tetrahydrofuran, the second basic regulator is potassium tert-butoxide, and the molar ratios of the 2, 5-thiophenedicarboxaldehyde, the 2, 5-furandicarbaldehyde or the compound X to the compound VI are all 0.4-0.6: 1; the molar ratio of the compound VI to the potassium tert-butoxide is 1: 0.1 to 1; the contact reaction temperature is 0-50 ℃ and the time is 6-24 h;
the reaction conditions of the steps in the second preparation method include the following:
in the step (1), the third organic solvent is acetone; the contact reaction temperature is 40-60 ℃ and the time is 20-30 h; the molar ratio of the compound I to the anhydrous potassium carbonate to the compound IV is 1:5-10: 1-2;
in the step (2), the sixth organic solvent is anhydrous tetrahydrofuran, the contact reaction temperature is-65 to-75 ℃, and the contact reaction time is 2 to 4 hours; the molar ratio of the compound VII, n-butyl lithium to dibromotetrachloroethane is 1:1-1.5: 1-3;
in the step (3), the fourth organic solvent is anhydrous xylene; the first catalyst is allylpalladium (II) chloride dimer; the second catalyst is 2-dicyclohexylphosphine-2 ',6' -dimethoxybiphenyl; the molar ratio of the first catalyst to the second catalyst to the compound VIII to the sodium acetonitrile acetate is 0.01-0.03: 0.03-0.1: 0.25-1: 1; the contact reaction temperature is 100-150 ℃, and the time is 10-15 h;
in the step (4), the fifth organic solvent is tetrahydrofuran, the third basic regulator is potassium tert-butoxide, and the molar ratio of the 2, 5-thiophenedicarboxaldehyde, the 2, 5-furandicarbaldehyde or the compound x to the compound ix is 0.4 to 0.6: 1; the molar ratio of the compound IX to potassium tert-butoxide is 1: 0.1 to 1; the contact reaction temperature is 0-50 ℃, and the reaction time is 6-24 h.
7. A reversibly light controllable, optically addressable, optically erasable, fluorescent/reflective dual mode transparent display device according to claim 2, wherein said nematic liquid crystal is selected from at least one of slc1717, E7, E44, E48, slc7011 and slc 1011.
8. An optically addressable optically erasable dual fluorescent/reflective transparent display device according to claim 1, wherein said polymer wall layer is made by a method comprising: and coating a mixture comprising an acrylate prepolymer, a photosensitive monomer and a photoinitiator on a transparent substrate, preheating, selectively exposing by ultraviolet, and finally washing an unpolymerized area by a developing solution to obtain the polymer wall layer.
9. An optically addressable light-erasable dual mode fluorescent/reflective transparent display device according to claim 8, wherein the photoactive monomer is at least one of a monofunctional acrylate photoactive monomer, a difunctional acrylate photoactive monomer, and a trifunctional acrylate photoactive monomer;
the monofunctional acrylate photosensitive monomer is isobornyl acrylate and/or 2-phenoxyethyl acrylate, the difunctional acrylate photosensitive monomer is 1, 6-hexanediol diacrylate and/or ethoxy bisphenol A dimethacrylate, and the trifunctional acrylate photosensitive monomer is ethoxy trimethylolpropane triacrylate;
the photoinitiator is α' -dimethylbenzyl ketal;
the mixing temperature of the mixture is 60-90 ℃; the preheating temperature is 60-90 ℃, and the preheating time is 1-2 h.
10. The optically addressable optically erasable dual mode fluorescent/reflective transparent display device of claim 1, wherein the first transparent substrate and the second transparent substrate are both transparent substrates that have been processed in anti-parallel.
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