Circular polarization room-temperature phosphorescent polymer film with adjustable afterglow color as well as preparation method and application of circular polarization room-temperature phosphorescent polymer film

Abstract

The invention discloses an afterglow-color-adjustable circularly-polarized room-temperature phosphorescent polymer film and a preparation method and application thereof, and the afterglow-color-adjustable circularly-polarized room-temperature phosphorescent polymer film is prepared by taking a chiral naphthalene phosphate derivative as an energy and chiral transfer donor and selecting a fluorescent dye rhodamine B (RB) as an acceptor. And co-doping with a polymer matrix to obtain the afterglow color adjustable circular polarization room-temperature phosphorescent polymer film. The obtained polymer film has good transparency, high room-temperature phosphorescence efficiency and asymmetric factors, accurately controllable multi-color afterglow and ultra-long afterglow life, which means that the polymer film has important application prospects in the fields of multiple anti-counterfeiting encryption and the like.

Description

[Technical field]

[0001] The invention relates to the technical field of organic optical materials and functional polymer materials, and in particular to a circularly polarized room temperature phosphorescent polymer film with adjustable afterglow color, and a preparation method and application thereof. [Background technology]

[0002] As a new type of optical functional material, circularly polarized luminescent (CPL) materials have attracted much attention due to their excellent optical sensitivity and spatial resolution. They have broad application prospects in 3D display, chiral sensors, optical information and data storage, asymmetric synthesis, bioimaging and other fields. Unlike unpolarized light, CPL can be obtained by chiral luminescent sources with inherent asymmetric molecular structures, or by using non-chiral molecules in a chiral environment. CPL materials have become a means to obtain circularly polarized emission efficiently without the need for polarizers. So far, various fluorescent CPL materials have been explored, but CPL materials with phosphorescent emission at room temperature have rarely been reported. Circularly polarized room temperature phosphorescent (CPP) materials have both chiral and triplet excited state characteristics, and have attracted widespread attention in advanced applications of 3D display and chiral optical devices. So far, the strategies for synthesizing CPPs mainly include chiral molecular engineering, cocrystals and supramolecular self-assembly.

[0003] Polymer-based CPP materials are popular due to their stretchability, flexibility and processability, and have made significant progress in improving the luminescence efficiency, phosphorescence lifetime and asymmetry factor of chiral materials. High-performance CPPs with tunable emission wavelengths have been achieved by mixing host and guest materials using the FRET and chiral transfer mechanisms. However, this approach usually requires a large amount of host and guest materials with precisely matched energy levels, which makes it impractical for practical applications. Therefore, how to conveniently tune the afterglow color of CPP materials remains a major challenge.

[0004] It is of great significance to develop a simple and effective method to precisely control the luminescence afterglow color of CPPs. [Summary of the invention]

[0005] Based on the existing technology Resonance energy transfer (FRET) and chiral transfer mechanisms achieve high-performance CPP with tunable emission wavelength by mixing host and guest materials. However, this method usually requires a large amount of host and guest materials with precisely matched energy levels. The present invention provides a circularly polarized room temperature phosphorescent polymer film with tunable afterglow color and a preparation method and application thereof. The present invention uses chiral naphthyl phosphate derivatives as energy and chiral transfer donors, selects fluorescent dye rhodamine B (RB) as an acceptor, and obtains a circularly polarized room temperature phosphorescent polymer film with tunable afterglow color by co-doping with a polymer matrix. The obtained polymer film has good transparency, high room temperature phosphorescence efficiency and asymmetry factor, precisely controllable multi-color afterglow and ultra-long afterglow life, which means that it has important application prospects in the fields of multiple anti-counterfeiting encryption and the like.

[0006] The technical principles of the present invention are as follows:

[0007] A chiral long-lasting phosphorescent material is used as the donor, and a common fluorescent dye is used as the acceptor. Under light excitation, a part of the triplet excitons of the chiral phosphorescent molecule will emit long-lasting room temperature phosphorescence (RTP), and the other part will induce the acceptor material to emit long-lasting circularly polarized fluorescence through FRET and chiral transfer. By adjusting the acceptor content, the intensity ratio of the long-lasting phosphorescence of the donor and the long-lasting fluorescence of the acceptor can be adjusted. Therefore, this method can accurately control multi-color circularly polarized afterglow, which has important application prospects in fields such as multiple anti-counterfeiting encryption.

[0008] The purpose of the present invention is achieved through the following technical solutions:

[0009] A circularly polarized room temperature phosphorescent polymer film with adjustable afterglow color, which is composed of a polymer matrix material, a donor material and an acceptor material;

[0010] The polymer matrix material is selected from one or more of polymethyl methacrylate (PMMA), polyvinyl alcohol (PVA), polyethylene (PP), polystyrene (PS), and polyamide (PA), and can be mixed in any proportion;

[0011] The donor material is selected from R / (S)-binaphthol phosphate, and its specific structure is shown in the following formulas Ⅰ and Ⅱ:

[0012]

[0013] The name of the naphthylphosphonic acid derivative in the above formula I is defined as S-BNDHP, and the corresponding polymer film is defined as S-BNDHP@PVA; the name of the naphthylphosphonic acid derivative in the above formula II is defined as R-BNDHP, and the corresponding polymer film is defined as R-BNDHP@PVA;

[0014] The receptor material is a fluorescent dye, and its specific structure is shown in the following formula III:

[0015]

[0016] It is stipulated that the fluorescent dye molecule Rhodamine B in the above formula III is referred to as RB; the polymer film corresponding to it and S-BNDHP is referred to as RB / S-BNDHP@PVA; the polymer film corresponding to it and R-BNDHP is referred to as RB / R-BNDHP@PVA;

[0017] The afterglow color-adjustable circularly polarized room temperature phosphorescent polymer film, wherein the polymer film has room temperature phosphorescence (RTP) properties, and under a 312nm excitation wavelength ultraviolet lamp at room temperature, the film color is blue, and after the ultraviolet lamp is turned off, it exhibits green, yellow-green, yellow, orange-yellow, orange, and red afterglow;

[0018] The afterglow color-adjustable circularly polarized room temperature phosphorescent polymer film is excited at an excitation wavelength of 312 nm. The doped films of RB / R-BNDHP@PVA and RB / S-BNDHP@PVA are measured to have perfect chiral symmetric CPL emission near 380 and 600 nm, with the g value reaching up to 5.17×10 -2 ; At the same time, the polymer film also showed a symmetrical absorption peak at 200-400nm in the CD spectrum;

[0019] The polymer film exhibits green, yellow-green, yellow, orange-yellow, orange, and red afterglow under 312nm ultraviolet light;

[0020] The afterglow color-adjustable circularly polarized room temperature phosphorescent polymer film has a phosphorescence emission wavelength of 501 and 534 nm for the S-BNDHP@PVA film at an excitation wavelength of 312 nm, and a phosphorescence lifetime of 1012.4 ms; the phosphorescence emission wavelength of 501 and 534 nm for the R-BNDHP@PVA film, and a phosphorescence lifetime of 1025.5 ms;

[0021] The circularly polarized room temperature phosphorescent polymer film with adjustable afterglow color can achieve multicolor afterglow changes from green to red after being doped with the fluorescent dye Rhodamine B (RB);

[0022] The afterglow color-adjustable circularly polarized room temperature phosphorescent polymer film has circularly polarized fluorescence (CPL) and circularly polarized phosphorescence (CPP) properties, and the asymmetry factor g value is as high as 5.17×10 -2 At the same time, the polymer film also showed a perfect chiral symmetric absorption peak in the CD spectrum.

[0023] The above-mentioned method for preparing a circularly polarized room temperature phosphorescent polymer film with adjustable afterglow color comprises the following steps:

[0024] (1) According to the proportion, 495 mg of the polymer matrix material is dissolved in 5 mL of a solvent to obtain a solution 1; the solvent is one of water, anhydrous ethanol, methanol and chloroform;

[0025] (2) dissolving 5 mg of naphthoic acid phosphate derivative S-BNDHP / R-BNDHP in 5 mL of an organic solvent to obtain a solution 2; the organic solvent is anhydrous ethanol or methanol;

[0026] (3) dissolving 0.0005-0.1 mg of the fluorescent dye molecule rhodamine B (RB) in 5 mL of an organic solvent to obtain a solution 3; the organic solvent is one of anhydrous ethanol and methanol;

[0027] (4) Solution 1 obtained in step (1) and solution 2 obtained in step (2) were mixed in a ratio of 495 mg:5 mg, and ultrasonically stirred to fully mix them to obtain a mixed solution 4;

[0028] (5) mixing solution 1 obtained in step (1), solution 2 obtained in step (2), and solution 3 obtained in step (3) in a ratio of 495 mg:5 mg:(0.0005-0.1) mg, and stirring by ultrasonic to fully mix them to obtain a mixed solution 5;

[0029] (6) pouring the mixed solution 4 obtained in step (4) into a culture dish, or pouring the mixed solution 5 obtained in step (5) into a culture dish, and placing it in an oven or in an air environment until the organic solvent and water are completely volatilized and a film is formed naturally, thereby obtaining a circularly polarized room temperature phosphorescent polymer film with adjustable afterglow color;

[0030] The polymer film exhibits green, yellow-green, yellow, orange-yellow, orange, and red afterglow under 312nm ultraviolet light;

[0031] When the polymer film is excited at an excitation wavelength of 312 nm, the emission peaks of the RB / R-BNDHP@PVA polymer film are 534, 534, 576, 578, 580 and 580 nm respectively; the emission peaks of the RB / S-BNDHP@PVA polymer film are 534, 534, 576, 578, 580 and 580 nm respectively; wherein the concentrations of rhodamine B (RB) are 0, 0.0005, 0.005, 0.025, 0.05 and 0.1 mg respectively, and the delay time is 0.2 ms;

[0032] When the polymer film is excited at an excitation wavelength of 312 nm, the lifetimes of the RB / R-BNDHP@PVA polymer film are 1025.5, 911.0, 896.8, 833.4, 737.9 and 637.5 nm, respectively; the lifetimes of the RB / S-BNDHP@PVA polymer film are 1012.4, 897.7, 891.1, 831.4, 724.3 and 610.5 ms, respectively; wherein the concentrations of rhodamine B (RB) are 0, 0.0005, 0.005, 0.025, 0.05 and 0.1 mg, respectively, the delay time is 0.2 ms, and the monitoring wavelength is 580 nm.

[0033] In step (3), 0.0005 mg, 0.005 mg, 0.025 mg, 0.05 mg, and 0.1 mg of the fluorescent dye molecule Rhodamine B (RB) were dissolved in 5 mL of an organic solvent, respectively.

[0034] The ultrasonic stirring time in step (4) and step (5) is 5 / 10 / 30 / 60 / 120 minutes.

[0035] The certain proportion in step (5) is 495 mg of the polymer matrix material, 5 mg of the naphthoic acid phosphate derivative S-BNDHP / R-BNDHP, and in solution 3 of step (5), the contents of rhodamine B are 0.0005, 0.005, 0.025, 0.05 and 0.1 mg respectively.

[0036] The oven in step (6) is a vacuum drying oven with a temperature of 40-65° C., a vacuum degree of 0.06-0.1 MPa, and a drying time of 2-12 hours.

[0037] The present invention also relates to the application of the above-mentioned afterglow color adjustable circularly polarized room temperature phosphorescent polymer film, specifically the multiple anti-counterfeiting and encryption applications of the polymer film, and the specific application range includes: light conversion film, ultraviolet light protection film, anti-counterfeiting encryption film, and multi-color circularly polarized display film.

[0038] Compared with the prior art, the present invention has the following advantages:

[0039] 1. The circularly polarized room temperature phosphorescent polymer film with adjustable afterglow color described in the present invention uses a chiral naphthyl phosphate derivative as an energy and chirality transfer donor and a fluorescent dye molecule rhodamine B (RB) as an acceptor, and can be directly co-doped with a polymer matrix to form a film in one step.

[0040] 2. The circularly polarized room temperature phosphorescent polymer film with adjustable afterglow color described in the present invention has a long life (seconds), high room temperature phosphorescence efficiency and asymmetry factor, and has a room temperature phosphorescent multi-color afterglow response at room temperature. The multi-color circularly polarized afterglow can be precisely controlled, which has important application prospects in the fields of multiple anti-counterfeiting encryption and the like.

[0041] 3. The circularly polarized room temperature phosphorescent polymer film with adjustable afterglow color described in the present invention has high transparency and good light transmittance in the visible light region, with a transmittance of more than 85%.

Brief Description of the Drawings

[0042] Figure 1 It is the S-BNDHP hydrogen nuclear magnetic spectrum described in Example 1 of the present invention (testing instrument: BrukerAV500 nuclear magnetic resonance spectrometer, solvent: deuterated dimethyl sulfoxide (DMSO-d6));

[0043] Figure 2 is the hydrogen nuclear magnetic spectrum of R-BNDHP described in Example 1 of the present invention (testing instrument: BrukerAV500 nuclear magnetic resonance spectrometer, solvent: deuterated dimethyl sulfoxide (DMSO-d6));

[0044] Figure 3 The following are photos of the polymer films (R-BNDHP@PVA and S-BNDHP@PVA) described in Example 1 of the present invention under indoor visible light and under 312nm ultraviolet light excitation (camera: Sony α7s);

[0045] Figure 4 is a spectrum of the transmittance of the polymer film in the ultraviolet-visible region described in Example 1 of the present invention, with a test wavelength range of 300-700 nm (testing instrument: PerkinElmer Lambda 365);

[0046] Figure 5 It is a graph of the phosphorescence decay curve of the polymer film (RB / R-BNDHP@PVA) described in Examples 1-6 of the present invention at an excitation wavelength of 312 nm (the monitoring emission wavelengths are 534 nm and 580 nm, respectively, and the delay time is 1 ms; the testing instrument: Edinburgh FLS1000);

[0047] Figure 6 is the XRD spectrum of the polymer film 0% RB / R-BNDHP@PVA described in Example 1 of the present invention (scanning range is 5-80°. Testing instrument: D8 DaVinci X-ray powder diffractometer);

[0048] Figure 7 It is a graph of the phosphorescence decay curve of the polymer film (RB / S-BNDHP@PVA) described in Examples 1-6 of the present invention at an excitation wavelength of 312 nm (the monitoring emission wavelengths are 534 nm and 580 nm, respectively, and the delay time is 1 ms; the testing instrument: Edinburgh FLS1000);

[0049] Figure 8It is the XRD spectrum of the polymer film 0% RB / S-BNDHP@PVA described in Example 1 of the present invention (scanning range is 5-80°; testing instrument: D8 DaVinci X-ray powder diffractometer);

[0050] Fig. 9 is a chiral circular polarization spectrum of the polymer film described in Examples 1-6 of the present invention (testing instrument: JASCOCPL-300);

[0051] Fig.10 is a spectrum of the asymmetry factor g value of the polymer film described in Examples 1-6 of the present invention (testing instrument: JASCO CPL-300);

[0052] Fig.11 is a CD spectrum of the polymer film described in Examples 1 to 6 of the present invention (testing instrument: JASCO J-1200);

[0053] Fig.12 It is a physical picture and schematic diagram of the application of the polymer film described in Examples 1-6 of the present invention in the field of multiple anti-counterfeiting encryption. [Specific implementation method]

[0054] The specific implementation modes of the present invention are further described below in conjunction with examples.

[0055] Embodiment 1:

[0056] A method for preparing a circularly polarized room temperature phosphorescent polymer film with adjustable afterglow color comprises the following steps:

[0057] The polymer matrix material component is commercially available granular polyvinyl alcohol (PVA-1788), and the donor component is: R-BNDHP / S-BNDHP, and the composition ratio is as follows by weight: polymer matrix material: 495 mg, donor component: 5 mg;

[0058] The method for preparing a circularly polarized room temperature phosphorescent polymer film with adjustable afterglow color is obtained by the following preparation process:

[0059] (1) Dissolving the donor component and the polymer matrix material with methanol and water respectively, mixing them in the above mass ratio and adding them to glass bottle 1, placing the obtained mixture in an ultrasonic bath for 5 minutes to fully mix them, and obtaining a mixed solution 1;

[0060] (2) Add the mixed solution 1 to the culture dish, transfer it to a vacuum drying oven, and dry it for 5 hours at a temperature of 55° C. and a vacuum degree of 0.1 MPa. Take it out after the organic solvent and water are completely evaporated.

[0061] Embodiment 2:

[0062] A method for preparing a circularly polarized room temperature phosphorescent polymer film with adjustable afterglow color comprises the following steps:

[0063] The polymer matrix material component is commercially available granular polyvinyl alcohol (PVA-1788), the donor component is: R-BNDHP / S-BNDHP, and the receptor component is: Rhodamine B (RB). The composition ratio is as follows by weight: polymer matrix material: 495 mg, donor component: 5 mg, receptor component: 0.0005 mg;

[0064] The method for preparing a circularly polarized room temperature phosphorescent polymer film with adjustable afterglow color is obtained by the following preparation process:

[0065] (1) Dissolving the donor component, the acceptor component and the polymer matrix material with methanol, methanol and water respectively, mixing them in the above mass ratio and adding them to glass bottle 2, placing the obtained mixture in ultrasound for 5 minutes to fully mix it, and obtaining a mixed solution 2;

[0066] (2) Add the mixed solution 2 to the culture dish, transfer it to a vacuum drying oven, and dry it for 5 hours at a temperature of 55° C. and a vacuum degree of 0.08 MPa. Take it out after the organic solvent and water are completely evaporated.

[0067] Embodiment 3:

[0068] A method for preparing a circularly polarized room temperature phosphorescent polymer film with adjustable afterglow color comprises the following steps:

[0069] The polymer matrix material component is commercially available granular polyvinyl alcohol (PVA-1788), the donor component is: R-BNDHP / S-BNDHP, and the receptor component is: Rhodamine B (RB). The composition ratio is as follows by weight: polymer matrix material: 495 mg, donor component: 5 mg, receptor component: 0.005 mg;

[0070] The method for preparing a circularly polarized room temperature phosphorescent polymer film with adjustable afterglow color is obtained by the following preparation process:

[0071] (1) Dissolving the donor component, the acceptor component and the polymer matrix material with methanol, methanol and water respectively, mixing them in the above mass ratio and adding them to a glass bottle 3, placing the obtained mixture in an ultrasonic bath for 5 minutes to fully mix it, and obtaining a mixed solution 3;

[0072] (2) Add the mixed solution 3 to the culture dish, transfer it to a vacuum drying oven, and dry it for 5 hours at a temperature of 55° C. and a vacuum degree of 0.1 MPa. Take it out after the organic solvent and water are completely evaporated.

[0073] Embodiment 4:

[0074] A method for preparing a circularly polarized room temperature phosphorescent polymer film with adjustable afterglow color comprises the following steps:

[0075] The polymer matrix material component is commercially available granular polyvinyl alcohol (PVA-1788), the donor component is: R-BNDHP / S-BNDHP, and the receptor component is: Rhodamine B (RB). The composition ratio is calculated by weight as follows: polymer matrix material: 495 mg, donor component: 5 mg, receptor component: 0.025 mg;

[0076] The method for preparing a circularly polarized room temperature phosphorescent polymer film with adjustable afterglow color is obtained by the following preparation process:

[0077] (1) Dissolving the donor component, the acceptor component and the polymer matrix material with methanol, methanol and water respectively, mixing them in the above mass ratio and adding them to a glass bottle 4, placing the obtained mixture in an ultrasonic bath for 5 minutes to fully mix it, and obtaining a mixed solution 4;

[0078] (2) Add the mixed solution 4 to the culture dish, transfer it to a vacuum drying oven, and dry it for 5 hours at a temperature of 55° C. and a vacuum degree of 0.1 MPa. Take it out after the organic solvent and water are completely evaporated.

[0079] Embodiment 5:

[0080] A method for preparing a circularly polarized room temperature phosphorescent polymer film with adjustable afterglow color comprises the following steps:

[0081] The polymer matrix material component is commercially available granular polyvinyl alcohol (PVA-1788), the donor component is: R-BNDHP / S-BNDHP, and the receptor component is: Rhodamine B (RB). The composition ratio is as follows by weight: polymer matrix material: 495 mg, donor component: 5 mg, receptor component: 0.05 mg;

[0082] The method for preparing a circularly polarized room temperature phosphorescent polymer film with adjustable afterglow color is obtained by the following preparation process:

[0083] (1) The donor component, the acceptor component and the polymer matrix material are dissolved in methanol, methanol and water respectively, mixed in the above mass ratio and added into a glass bottle 5, and the obtained mixture is placed in an ultrasonic bath for 5 minutes to be fully mixed, thereby obtaining a mixed solution 5.

[0084] (2) Add the mixed solution 5 to the culture dish, transfer it to a vacuum drying oven, and dry it for 6 hours at a temperature of 55° C. and a vacuum degree of 0.09 MPa. Take it out after the organic solvent and water are completely evaporated.

[0085] Embodiment 6:

[0086] A method for preparing a circularly polarized room temperature phosphorescent polymer film with adjustable afterglow color comprises the following steps:

[0087] The polymer matrix material component is commercially available granular polyvinyl alcohol (PVA-1788), the donor component is: R-BNDHP / S-BNDHP, and the receptor component is: Rhodamine B (RB). The composition ratio is as follows by weight: polymer matrix material: 495 mg, donor component: 5 mg, receptor component: 0.1 mg;

[0088] The method for preparing a circularly polarized room temperature phosphorescent polymer film with adjustable afterglow color is obtained by the following preparation process:

[0089] (1) Dissolve the donor component, the acceptor component and the polymer matrix material with methanol, methanol and water respectively, mix them according to the above mass ratio and add them into glass bottle 6, and place the obtained mixture in ultrasound for 5 minutes to fully mix it to obtain a mixed solution 6;

[0090] (2) Add the mixed solution 6 to the culture dish, transfer it to a vacuum drying oven, and dry it for 6 hours at a temperature of 55° C. and a vacuum degree of 0.08 MPa. Take it out after the organic solvent and water are completely evaporated.

[0091] Experimental Example 1:

[0092] Experimental study on the transmittance performance of polymer films in the UV-visible region:

[0093] Mix 5 mg of R-BNDHP / S-BNDHP ethanol solution and 495 mg of polyvinyl alcohol aqueous solution to obtain a mixed solution of R-BNDHP@PVA / S-BNDH@PVA; ultrasonicate the mixed solution for 30 minutes to fully mix it; let the mixed solution stand at room temperature for 30-60 minutes to remove bubbles; quickly drop the obtained mixed solution on a culture dish, transfer it to a vacuum drying oven and dry it at 55°C for 4-8 hours with a vacuum degree of 0.1MPa. After the organic solvent and water are completely volatilized, take it out and let it cool naturally to obtain a 1% R-BNDHP@PVA / S-BNDH@PVA doped film with a mass ratio of 1:100; Figure 3 As shown in the above picture, it is colorless and transparent under indoor visible light (S-BNDHP@PVA on the left and R-BNDHP@PVA on the right). Figure 3 The polymer film of 1% R-BNDHP@PVA / S-BNDH@PVA shown in the figure below appears blue under 312nm UV light (S-BNDHP@PVA on the left and R-BNDHP@PVA on the right);

[0094] In order to further study the light transmittance performance of R-BNDHP@PVA / S-BNDH@PVA doped films, the transmittance was measured using a PerkinElmer Lambda 365 UV-visible spectrophotometer, as shown in Figure 2 . Figure 4 As shown in the figure, the 1% R-BNDHP@PVA / S-BNDH@PVA doped film has good anti-transmission ability in the ultraviolet light region and good transmittance in the visible light region, indicating that the 1% R-BNDHP@PVA / S-BNDH@PVA doped film can absorb ultraviolet light well and transmit visible light, and has good light transmittance performance.

[0095] Experimental Example 2:

[0096] Experimental study on the luminescence properties of RB / R-BNDHP@PVA polymer film:

[0097] Mix 0, 0.0005, 0.005, 0.025, 0.05 and 0.1 mg of rhodamine B (RB) ethanol solution (one of them), 5 mg of R-BNDHP ethanol solution and 495 mg of polyvinyl alcohol (PVA) aqueous solution to obtain a mixed solution of RB / R-BNDHP@PVA; ultrasonicate the mixed solution for 30 minutes to fully mix it; let the mixed solution stand at room temperature for 30-60 minutes to remove bubbles; quickly drop the obtained mixed solution on a culture dish, transfer it to a vacuum drying oven and dry it at 40-65°C for 2-12 hours with a vacuum degree of 0.06-0.1MPa, wait until the organic solvent and water are completely volatilized, take it out and let it cool naturally, and then RB / R-BNDHP@PVA doped films with RB and R-BNDHP mass ratios of 0%, 0.01%, 0.1%, 0.5%, 1% and 2% respectively can be obtained;

[0098] In order to study the photophysical properties of the doped films, the phosphorescence emission spectra, phosphorescence decay curves and quantum yields of the multi-color doped films were tested using an Edinburgh FLS1000 photoluminescence spectrometer. Figure 5 As shown in the upper right figure, it is the phosphorescence emission spectra of 0%, 0.01%, 0.1%, 0.5%, 1% and 2% RB / R-BNDHP@PVA doped films. Under the excitation wavelength of 312nm, the delay time is 0.2ms, and the measured phosphorescence emission peaks are at 534, 534, 576, 578, 580 and 580nm respectively; by comparing the emission peak intensity of 580nm and 534nm, it can be observed that with the increase of the content of rhodamine B (RB), the ratio continues to increase, so that the multi-color luminescence afterglow can be precisely controlled; Figure 5The lower right figure shows the phosphorescence decay curves of 0%, 0.01%, 0.1%, 0.5%, 1% and 2% RB / R-BNDHP@PVA doped films. The excitation wavelength is 312nm and the detection wavelength is 580nm. The calculated phosphorescence lifetimes are 1025.5, 911.0, 896.8, 833.4, 737.9 and 637.5ms, respectively. The photoluminescence quantum efficiency of 0% RB / R-BNDHP@PVA film was also tested to be 41.43%, and the phosphorescence quantum efficiency was 14.23%. Figure 6 The XRD pattern of 0% RB / R-BNDHP@PVA film is shown, indicating that the film contains a small amount of crystalline structure and is uniformly dispersed in the film.

[0099] Experimental Example 3:

[0100] Experimental study on the luminescence properties of RB / S-BNDHP@PVA polymer film:

[0101] Mix 0, 0.0005, 0.005, 0.025, 0.05 and 0.1 mg of rhodamine B (RB) ethanol solution (one of them), 5 mg of S-BNDHP ethanol solution and 495 mg of polyvinyl alcohol (PVA) aqueous solution to obtain a mixed solution of RB / S-BNDHP@PVA; ultrasonicate the mixed solution for 30 minutes to fully mix it; let the mixed solution stand at room temperature for 30-60 minutes to remove bubbles; quickly drop the obtained mixed solution on a culture dish, transfer it to a vacuum drying oven and dry it at 40-65°C for 2-12 hours with a vacuum degree of 0.06-0.1MPa, wait until the organic solvent and water are completely volatilized, take it out and let it cool naturally, and then RB / S-BNDHP@PVA doped films with RB and S-BNDHP mass ratios of 0%, 0.01%, 0.1%, 0.5%, 1% and 2% respectively can be obtained;

[0102] In order to study the photophysical properties of the doped films, the phosphorescence emission spectra, phosphorescence decay curves and quantum yields of the multi-color doped films were tested using an Edinburgh FLS1000 photoluminescence spectrometer. Figure 7 As shown in the upper right figure, it is the phosphorescence emission spectra of 0%, 0.01%, 0.1%, 0.5%, 1% and 2% RB / S-BNDHP@PVA doped films. Under the excitation wavelength of 312nm, the delay time is 0.2ms, and the measured phosphorescence emission peaks are at 534, 534, 576, 578, 580 and 580nm respectively; by comparing the emission peak intensity of 580nm and 534nm, it can be observed that with the increase of the content of rhodamine B (RB), the ratio continues to increase, so that the multi-color luminescence afterglow can be precisely controlled; Figure 7The lower right figure shows the phosphorescence decay curves of 0%, 0.01%, 0.1%, 0.5%, 1% and 2% RB / S-BNDHP@PVA doped films. The excitation wavelength is 312nm and the detection wavelength is 580nm. The calculated phosphorescence lifetimes are 1012.4, 897.7, 891.1, 831.4, 724.3 and 610.5ms, respectively. The photoluminescence quantum efficiency of 0% RB / S-BNDHP@PVA film was also tested to be 44.49%, and the phosphorescence quantum efficiency was 13.02%. Figure 8 The XRD pattern of 0% RB / S-BNDHP@PVA film is shown, indicating that the film contains a small amount of crystalline structure and is uniformly dispersed in the film.

[0103] Experimental Example 4:

[0104] Experimental study on circularly polarized luminescence properties of polymer films:

[0105] 0, 0.0005, 0.005, 0.025, 0.05 and 0.1 mg of rhodamine B (RB) ethanol solution (one of them), 5 mg of R-BNDHP / S-BNDHP ethanol solution and 495 mg of polyvinyl alcohol (PVA) aqueous solution were mixed to obtain a mixed solution of RB / R-BNDHP@PVA and RB / S-BNDHP@PVA; the mixed solution was ultrasonicated for 30 minutes to be fully mixed; the mixed solution was allowed to stand at room temperature for 30-6 0 minutes to remove bubbles; quickly drop the obtained mixed solution on the culture dish, transfer it to a vacuum drying oven and dry it at 40-65°C for 2-12 hours with a vacuum degree of 0.06-0.1MPa, wait for the organic solvent and water to completely evaporate, take it out and let it cool naturally, then RB / R-BNDHP@PVA and RB / S-BNDHP@PVA doped films with RB and R-BNDHP / S-BNDHP mass ratios of 0%, 0.01%, 0.1%, 0.5%, 1% and 2% respectively can be obtained;

[0106] In order to study the photophysical properties of the doped films, the circularly polarized emission spectra of the multicolor doped films were tested using a JASCO CPL-300 circular polarization spectrometer. Fig. 9 As shown in the figure, the CPL spectra of 0%, 0.01%, 0.1%, 0.5%, 1% and 2% RB / R-BNDHP@PVA and RB / S-BNDHP@PVA doped films are obtained. Under the excitation wavelength of 312nm, the CPL emission peaks near 380 and 600nm are measured. The spectra of RB / R-BNDHP@PVA and RB / S-BNDHP@PVA show perfect chiral symmetry. With the increase of RB content, the circular polarization signal at 600nm increases continuously, so that the multi-color chiral luminescence afterglow can be precisely controlled. Fig.10 As shown in the figure, the asymmetry factor g value spectra of 0%, 0.01%, 0.1%, 0.5%, 1% and 2% RB / R-BNDHP@PVA and RB / S-BNDHP@PVA doped films are shown. It can be observed that the g value can reach up to 5.17×10 -2 This is conducive to the application in the field of multiple anti-counterfeiting encryption, and is expected to become a new type of chiral circular polarization film material with high g value; In addition, the circular polarization CD spectrum of the multi-color doped film was tested using the JASCO J-1500, such as Fig.11 As shown, the CD spectra of 0%, 0.01%, 0.1%, 0.5%, 1% and 2% RB / R-BNDHP@PVA and RB / S-BNDHP@PVA doped films show symmetrical absorption peaks in the CD spectra of R-BNDHP and S-BNDHP multicolor films. In summary, it shows that the adjustable multicolor chiral film has been successfully developed and the film has obvious chiral characteristics.

[0107] Experimental Example 5:

[0108] Research on multiple anti-counterfeiting encryption applications of polymer films:

[0109] RB / R-BNDHP@PVA and RB / S-BNDHP@PVA doped films with different mass ratios (including 0%, 0.01%, 0.1%, 0.5%, 1% and 2%) were made into four 3×4 dot matrices, and the green afterglow was defined as valid information and other colors as invalid information; Fig.12 As shown in a, it emits blue and other multi-color fluorescence under 312nm ultraviolet light, and emits green, yellow and orange-red afterglow at room temperature after turning off the ultraviolet light; the resulting pattern shows an anti-counterfeiting encrypted information pattern (key 1); after 4.5 seconds, the second layer of encrypted information pattern (key 2) is displayed; a polarizer is added at 4.5 seconds to obtain an R-chirality encrypted information pattern (key 3); in addition, as Fig.12 As shown in b, the first layer of encrypted information of R chirality and S chirality are combined, marked with binary 0 and 1 (R is marked as 1 and S is marked as 0), and then converted into decimal to obtain the final anti-counterfeiting encryption answer.

[0110] The above is an explanation of the embodiments of the present invention. However, the present invention is not limited to the above embodiments. Any changes within the spirit and principle of the present invention and without departing from the conceptual framework of the present invention should be included in the protection scope of the present invention.

Claims

1. A circularly polarized room temperature phosphorescent polymer film with adjustable afterglow color, characterized in that: Its composition is a polymer matrix material, a donor material and an acceptor material; The polymer matrix material is selected from one or more of polymethyl methacrylate, polyvinyl alcohol, polyethylene, polystyrene, and polyamide, and can be mixed in any proportion; The donor material is selected from R / (S)-binaphthol phosphate, and its specific structure is shown in the following formulas Ⅰ and Ⅱ: The name of the naphthylphosphonic acid derivative in the above formula I is defined as S-BNDHP, and the corresponding polymer film is defined as S-BNDHP@PVA; the name of the naphthylphosphonic acid derivative in the above formula II is defined as R-BNDHP, and the corresponding polymer film is defined as R-BNDHP@PVA; The receptor material is a fluorescent dye, and its specific structure is shown in the following formula III: It is stipulated that the fluorescent dye molecule Rhodamine B in the above formula III is referred to as RB; the polymer film corresponding to it and S-BNDHP is referred to as RB / S-BNDHP@PVA; the polymer film corresponding to it and R-BNDHP is referred to as RB / R-BNDHP@PVA; The afterglow color-adjustable circularly polarized room temperature phosphorescent polymer film, wherein the polymer film has room temperature phosphorescence (RTP) properties, and under a 312nm excitation wavelength ultraviolet lamp at room temperature, the film color is blue, and after the ultraviolet lamp is turned off, it exhibits green, yellow-green, yellow, orange-yellow, orange, and red afterglow; The afterglow color-adjustable circularly polarized room temperature phosphorescent polymer film was excited at an excitation wavelength of 312 nm. The doped films of RB / R-BNDHP@PVA and RB / S-BNDHP@PVA were measured to have perfect chiral symmetric CPL emission near 380 and 600 nm, with the highest g value reaching 5.17×10 -2 ; At the same time, the polymer film also showed a symmetrical absorption peak at 200-400nm in the CD spectrum; The polymer film exhibits green, yellow-green, yellow, orange-yellow, orange, and red afterglow under 312nm ultraviolet light; The circularly polarized room temperature phosphorescent polymer film with adjustable afterglow color has a phosphorescence emission wavelength of 501 and 534 nm for the S-BNDHP@PVA film at an excitation wavelength of 312 nm, and a phosphorescence lifetime of 1012.4 ms; the phosphorescence emission wavelength of the R-BNDHP@PVA film is 501 and 534 nm, and a phosphorescence lifetime of 1025.5 ms; The circularly polarized room temperature phosphorescent polymer film with adjustable afterglow color, after being doped with the fluorescent dye Rhodamine B, realizes a multi-color afterglow change from green to red light; The afterglow color-adjustable circularly polarized room temperature phosphorescent polymer film has circularly polarized fluorescence and circularly polarized phosphorescence properties, and the asymmetry factor g value is as high as 5.17×10 -2 At the same time, the polymer film also showed a perfect chiral symmetric absorption peak in the CD spectrum.

2. The method for preparing a circularly polarized room temperature phosphorescent polymer film with adjustable afterglow color according to claim 1, characterized in that: The steps include: (1) According to the proportion, 495 mg of the polymer matrix material is dissolved in 5 mL of a solvent to obtain a solution 1; the solvent is one of water, anhydrous ethanol, methanol and chloroform; (2) dissolving 5 mg of naphthoic acid phosphate derivative S-BNDHP / R-BNDHP in 5 mL of an organic solvent to obtain a solution 2; the organic solvent is anhydrous ethanol or methanol; (3) dissolving the fluorescent dye molecule Rhodamine B (0.0005-0.1) mg in 5 mL of an organic solvent to obtain a solution 3; the organic solvent is one of anhydrous ethanol and methanol; (4) Solution 1 obtained in step (1) and solution 2 obtained in step (2) were mixed in a ratio of 495 mg:5 mg, and ultrasonically stirred to fully mix them to obtain a mixed solution 4; (5) mixing solution 1 obtained in step (1), solution 2 obtained in step (2), and solution 3 obtained in step (3) in a ratio of 495 mg:5 mg:(0.0005-0.1) mg, and stirring by ultrasonic to fully mix them to obtain a mixed solution 5; (6) pouring the mixed solution 4 obtained in step (4) into a culture dish, or pouring the mixed solution 5 obtained in step (5) into a culture dish, and placing it in an oven or in an air environment until the organic solvent and water are completely volatilized and a film is formed naturally, thereby obtaining a circularly polarized room temperature phosphorescent polymer film with adjustable afterglow color; The polymer film exhibits green, yellow-green, yellow, orange-yellow, orange, and red afterglow under 312nm ultraviolet light; When the polymer film is excited at an excitation wavelength of 312 nm, the emission peaks of the RB / R-BNDHP@PVA polymer film are 534, 534, 576, 578, 580 and 580 nm respectively; the emission peaks of the RB / S-BNDHP@PVA polymer film are 534, 534, 576, 578, 580 and 580 nm respectively; wherein the rhodamine B is 0, 0.0005, 0.005, 0.025, 0.05 and 0.1 mg respectively, and the delay time is 0.2 ms; When the polymer film is excited at an excitation wavelength of 312 nm, the lifetimes of the RB / R-BNDHP@PVA polymer film are 1025.5, 911.0, 896.8, 833.4, 737.9 and 637.5 nm, respectively; the lifetimes of the RB / S-BNDHP@PVA polymer film are 1012.4, 897.7, 891.1, 831.4, 724.3 and 610.5 ms, respectively; wherein the rhodamine B is 0, 0.0005, 0.005, 0.025, 0.05 and 0.1 mg, respectively, the delay time is 0.2 ms, and the monitoring wavelength is 580 nm.

3. The method for preparing a circularly polarized room temperature phosphorescent polymer film with adjustable afterglow color according to claim 2, characterized in that: In step (3), 0.0005 mg, 0.005 mg, 0.025 mg, 0.05 mg, and 0.1 mg of the fluorescent dye molecule Rhodamine B were dissolved in 5 mL of an organic solvent, respectively.

4. The method for preparing a circularly polarized room temperature phosphorescent polymer film with adjustable afterglow color according to claim 2, characterized in that: The ultrasonic stirring time in step (4) and step (5) is 5 minutes, 10 minutes, 30 minutes, 60 minutes, and 120 minutes.

5. The method for preparing a circularly polarized room temperature phosphorescent polymer film with adjustable afterglow color according to claim 2, characterized in that: In solution 3 of step (5), the amounts of rhodamine B were 0.0005, 0.005, 0.025, 0.05 and 0.1 mg respectively.

6. The method for preparing a circularly polarized room temperature phosphorescent polymer film with adjustable afterglow color according to claim 2, characterized in that: The oven in step (6) is a vacuum drying oven with a temperature of 40-65° C., a vacuum degree of 0.06-0.1 MPa, and a drying time of 2-12 hours.

7. The use of a circularly polarized room temperature phosphorescent polymer film with adjustable afterglow color as claimed in claim 1, characterized in that: The polymer film is applied to multiple anti-counterfeiting and encryption, and its application scope includes: light-converting film, ultraviolet light protection film, anti-counterfeiting and encryption film, and multi-color circular polarization display film.

Images