Polypropylene-based organic light-emitting material, and preparation method and application thereof

Abstract

The application discloses a kind of polypropylene-based organic luminescent materials and preparation method and application thereof.The composition of polypropylene-based organic luminescent material of the application includes polypropylene, layered silicate and organic dye.The preparation method of polypropylene-based organic luminescent material of the application includes the following steps: polypropylene, layered silicate and organic dye are mixed to carry out melt processing, then cooling forming is carried out, and polypropylene-based organic luminescent material is obtained.The polypropylene-based organic luminescent material of the application has excellent luminescent performance, excellent processing performance, low cost and other advantages, can be used in display, biological imaging, anti-fake encryption and other fields, and its preparation method is simple in operation, mild in process condition, low in equipment requirement, suitable for large-scale industrial production and application.

Description

Technical Field

[0001] This invention relates to the field of organic light-emitting technology, specifically to a polypropylene-based organic light-emitting material, its preparation method, and its application. Background Technology

[0002] Polymer-based luminescent materials are luminescent materials prepared by introducing luminescent units into polymers. They possess advantages such as good flexibility, stretchability, ease of processing, and high thermal stability, and have broad application prospects in fields such as displays, bioimaging, and anti-counterfeiting encryption. It is well known that materials exhibiting "multi-mode luminescence" characteristics, such as phosphorescence, thermally activated delayed fluorescence (TADF), and doublet exciton luminescence, have a wider range of applications compared to materials with only single-mode fluorescence. However, most existing phosphorescent materials are heavy metals such as zinc sulfide and rare earth oxides, which suffer from high cost, high toxicity, and complex preparation conditions. TADF and doublet exciton luminescent materials, on the other hand, have limited variety and high synthesis costs. These limitations significantly restrict the preparation and practical application of existing materials with "multi-mode luminescence" characteristics.

[0003] Studies have shown that dispersing small organic molecule luminescent materials in a polymer matrix through physical blending can yield functional polymeric materials with photoluminescent properties. In these materials, the polymer matrix provides a rigid environment for the luminescent material, suppressing non-radiative transitions and blocking oxygen to prevent the quenching of high-spin excitons. Therefore, the polymer matrix plays a crucial role in the luminescent performance of these polymer-based luminescent materials. Currently, polymer-based luminescent materials mainly use polymers such as polyvinyl alcohol and polymethyl methacrylate as matrices. However, polypropylene, as the world's largest-volume, lowest-cost, and most widely used single-strand polymer, has not yet been used in "multimode luminescence" materials. The main reasons for this are as follows: 1) Polypropylene molecular chains are relatively soft and have a low glass transition temperature, so they cannot provide a rigid environment to suppress non-radiative transitions; 2) The polypropylene molecular chains are not tightly packed, resulting in poor gas barrier properties, making it difficult to suppress the quenching of excitons by oxygen.

[0004] Therefore, developing a polypropylene-based organic light-emitting material with excellent luminescence properties, excellent processing properties, and low cost is of great significance. Summary of the Invention

[0005] The purpose of this invention is to provide a polypropylene-based organic light-emitting material, its preparation method, and its application.

[0006] The technical solution adopted in this invention is:

[0007] A polypropylene-based organic light-emitting material, comprising polypropylene, layered silicate, and organic dye.

[0008] Preferably, the number-average molecular weight of the polypropylene is 200,000 g / mol to 600,000 g / mol.

[0009] Preferably, the layered silicate is at least one selected from montmorillonite, bentonite, kaolinite, lithium montmorillonite, and halloysite.

[0010] Preferably, the layered silicate has a mass percentage content of 5% to 15% in the polypropylene-based organic light-emitting material.

[0011] More preferably, the layered silicate has a mass percentage content of 7% to 10% in the polypropylene-based organic light-emitting material.

[0012] Preferably, the organic dye is at least one selected from β-diketone boron fluorine complex (BF2dbm), carbazole (Cz), 1,8-naphthalenedicarboxylic anhydride (NA), terephthalic acid (p-PA), 4,4-dibromobiphenyl (Dbb), and 2,4,6-trihydroxypyrimidine (BA).

[0013] The structural formulas of organic dyes are shown below:

[0014]

[0015] Preferably, the organic dye has a mass percentage content of 0.1% to 10% in the polypropylene-based organic light-emitting material.

[0016] More preferably, the organic dye has a mass percentage content of 1% to 5% in the polypropylene-based organic light-emitting material.

[0017] A method for preparing a polypropylene-based organic light-emitting material as described above includes the following steps: mixing polypropylene, layered silicate and organic dye for melt processing, and then cooling and molding to obtain the polypropylene-based organic light-emitting material.

[0018] Preferably, the melt processing is carried out at a temperature of 150°C to 250°C.

[0019] More preferably, the melt processing is carried out at a temperature of 175°C to 185°C.

[0020] Preferably, the product obtained by the cooling molding is in the form of granules, threads, or films.

[0021] Applications of a polypropylene-based organic light-emitting material as described above in the fields of display, bioimaging, or anti-counterfeiting and encryption.

[0022] The beneficial effects of the present invention are: the polypropylene-based organic light-emitting material of the present invention has the advantages of excellent light-emitting performance, excellent processing performance, and low cost, and can be used in fields such as display, bio-imaging, anti-counterfeiting encryption, etc. Moreover, its preparation method is simple to operate, the process conditions are mild, and the equipment requirements are low, making it suitable for large-scale industrial production and application.

[0023] Specifically:

[0024] 1) The polypropylene-based organic light-emitting material of the present invention contains layered silicates, which can improve the rigidity of polypropylene molecular chain segments and block oxygen to avoid exciton quenching, thus effectively solving the problem that high spin state light emission is difficult to achieve in polypropylene.

[0025] 2) The polypropylene-based organic light-emitting material of the present invention has "multi-mode light emission" performance. It has dual light emission performance of fluorescence and phosphorescence at room temperature. Fluorescence and delayed light emission can be observed simultaneously on the same material (fluorescence can be observed when excited by ultraviolet lamp, and afterglow lasting for several seconds can be observed after the ultraviolet lamp is turned off). It has a very broad application prospect in the fields of anti-counterfeiting, information storage, and information encryption.

[0026] 3) The polypropylene-based organic light-emitting material of the present invention has good processing performance and can be processed by existing polymer processing equipment such as granulation, injection molding, film stretching, and blown film blowing, thereby ensuring the application of polypropylene-based organic light-emitting material in a wide range of scenarios;

[0027] 4) The raw materials for the polypropylene-based organic light-emitting materials of the present invention are inexpensive and readily available, thus providing a way for the large-scale, low-cost production and application of functional polypropylene materials. Attached Figure Description

[0028] Figure 1 The figures show the luminescence effect test results of the polypropylene-based organic light-emitting materials of Examples 1-4 and the comparative examples under ultraviolet light irradiation and after the ultraviolet light was turned off.

[0029] Figure 2 This is the delayed emission spectrum of the polypropylene-based organic light-emitting material in Example 1.

[0030] Figure 3 This is the delayed emission spectrum of the polypropylene-based organic light-emitting material in Example 2.

[0031] Figure 4 This is the delayed emission spectrum of the polypropylene-based organic light-emitting material in Example 3.

[0032] Figure 5 This is the delayed emission spectrum of the polypropylene-based organic light-emitting material in Example 4. Detailed Implementation

[0033] The present invention will be further explained and described below with reference to specific embodiments.

[0034] Example 1:

[0035] A polypropylene-based organic light-emitting material is prepared by the following method:

[0036] Polypropylene (number average molecular weight of 450,000 g / mol), montmorillonite powder and carbazole are added to a screw extruder at a mass ratio of 90:9:1, blended at 180°C, and then extruded and cooled to form polypropylene-based organic light-emitting materials (wires).

[0037] Performance testing:

[0038] The luminescence effect test results of the polypropylene-based organic light-emitting material in this embodiment under ultraviolet light irradiation (UV On) and after ultraviolet light is turned off (UV Off) are shown in the figure below. Figure 1 As shown in (a) of the figure, the delayed emission spectrum (delay time is 10 ms) is as follows. Figure 2 As shown.

[0039] Depend on Figure 1 and Figure 2 It can be seen that polypropylene-based organic light-emitting materials can exhibit blue fluorescence under ultraviolet light excitation, and can continue to emit green afterglow after the ultraviolet lamp is turned off, with a duration of about 6 seconds and an emission wavelength of 498 nm.

[0040] Example 2:

[0041] A polypropylene-based organic light-emitting material is prepared by the following method:

[0042] Polypropylene (number average molecular weight of 450,000 g / mol), montmorillonite powder and carbazole are added to a screw extruder in a mass ratio of 90:7:3, blended at 180°C, and then extruded and cooled to form polypropylene-based organic light-emitting materials (wires).

[0043] Performance testing:

[0044] The luminescence effect test results of the polypropylene-based organic light-emitting material in this embodiment under ultraviolet light irradiation (UV On) and after ultraviolet light is turned off (UV Off) are shown in the figure below. Figure 1 As shown in (b) of the figure, the delayed emission spectrum (delay time is 10ms) is as follows. Figure 3 As shown.

[0045] Depend on Figure 1 and Figure 3 It can be seen that polypropylene-based organic light-emitting materials can exhibit blue fluorescence under ultraviolet light excitation, and can continue to emit green afterglow after the ultraviolet lamp is turned off, with a duration of about 6 seconds and an emission wavelength of 498 nm.

[0046] Example 3:

[0047] A polypropylene-based organic light-emitting material is prepared by the following method:

[0048] Polypropylene (number average molecular weight of 450,000 g / mol), montmorillonite powder and 4,4-dibromobiphenyl were added to a screw extruder in a mass ratio of 89:8:3, blended at 180°C, and then extruded and cooled to form polypropylene-based organic light-emitting materials (wires).

[0049] Performance testing:

[0050] The luminescence effect test results of the polypropylene-based organic light-emitting material in this embodiment under ultraviolet light irradiation (UV On) and after ultraviolet light is turned off (UV Off) are shown in the figure below. Figure 1 As shown in (c) of the figure, the delayed emission spectrum (delay time is 10ms) is as follows. Figure 4 As shown.

[0051] Depend on Figure 1 and Figure 4 It can be seen that polypropylene-based organic light-emitting materials can exhibit blue fluorescence under ultraviolet light excitation, and can continue to emit green afterglow after the ultraviolet lamp is turned off, with a duration of about 5 seconds and an emission wavelength of 495nm.

[0052] Example 4:

[0053] A polypropylene-based organic light-emitting material is prepared by the following method:

[0054] Polypropylene (number average molecular weight of 450,000 g / mol), bentonite and carbazole were added to a screw extruder in a mass ratio of 87:8:5, blended at 180°C, and then extruded and cooled to form polypropylene-based organic light-emitting materials (wires).

[0055] Performance testing:

[0056] The luminescence effect test results of the polypropylene-based organic light-emitting material in this embodiment under ultraviolet light irradiation (UV On) and after ultraviolet light is turned off (UV Off) are shown in the figure below. Figure 1 As shown in (d) of the figure, the delayed emission spectrum (delay time is 10ms) is as follows. Figure 5 As shown.

[0057] Depend on Figure 1 and Figure 5 It can be seen that polypropylene-based organic light-emitting materials can exhibit blue fluorescence under ultraviolet light excitation, and can continue to emit green afterglow after the ultraviolet lamp is turned off, with a duration of about 5 seconds and an emission wavelength of 495nm.

[0058] Example 5:

[0059] A polypropylene-based organic light-emitting material is prepared by the following method:

[0060] Polypropylene (number average molecular weight of 450,000 g / mol), kaolinite powder and terephthalic acid are added to a screw extruder in a mass ratio of 90:7:3, blended at 180°C, and then extruded and cooled to form polypropylene-based organic light-emitting materials (wires).

[0061] According to the test (the test method is the same as in Example 1), the polypropylene-based organic light-emitting material of this example can be observed to emit blue fluorescence under ultraviolet light excitation, and can continue to emit green afterglow after the ultraviolet lamp is turned off, with a duration of about 5 seconds and an emission wavelength of 475nm.

[0062] Example 6:

[0063] A polypropylene-based organic light-emitting material is prepared by the following method:

[0064] Polypropylene (number average molecular weight of 530,000 g / mol), halloysite powder and 2,4,6-trihydroxypyrimidine were added to a screw extruder in a mass ratio of 90:7:3, blended at 180°C, and then extruded and cooled to form polypropylene-based organic light-emitting materials (wires).

[0065] According to the test (the test method is the same as in Example 1), the polypropylene-based organic light-emitting material of this example can be observed to emit blue fluorescence under ultraviolet light excitation, and can continue to emit green afterglow after the ultraviolet lamp is turned off, with a duration of about 3 seconds and an emission wavelength of 497nm.

[0066] Example 7:

[0067] A polypropylene-based organic light-emitting material is prepared by the following method:

[0068] Polypropylene (number average molecular weight of 530,000 g / mol), lithium montmorillonite powder and 2,4,6-trihydroxypyrimidine were added to a casting machine at a mass ratio of 87:10:3, and then blended and extruded at 180°C to obtain polypropylene-based organic light-emitting material (sheet).

[0069] According to the test (the test method is the same as in Example 1), the polypropylene-based organic light-emitting material of this example can be observed to emit blue fluorescence under ultraviolet light excitation, and can continue to emit green afterglow after the ultraviolet lamp is turned off, with a duration of about 3 seconds and an emission wavelength of 497nm.

[0070] Example 8:

[0071] A polypropylene-based organic light-emitting material is prepared by the following method:

[0072] Polypropylene (number average molecular weight of 530,000 g / mol), montmorillonite powder and carbazole were added to a casting machine at a mass ratio of 84:12:4, and then blended and extruded at 180°C to obtain polypropylene-based organic light-emitting material (sheet).

[0073] According to the test (the test method is the same as in Example 1), the polypropylene-based organic light-emitting material of this example can be observed to emit blue fluorescence under ultraviolet light excitation, and can continue to emit green afterglow after the ultraviolet lamp is turned off, with a duration of about 3 seconds and an emission wavelength of 520nm.

[0074] Comparative example:

[0075] A polypropylene-based organic light-emitting material is prepared by the following method:

[0076] Polypropylene (number average molecular weight of 450,000 g / mol) and carbazole were added to a screw extruder at a mass ratio of 97:3, blended at 180°C, and then extruded and cooled to form polypropylene-based organic light-emitting materials (wires).

[0077] Performance testing:

[0078] The luminescence effect test results of the polypropylene-based organic light-emitting material in this comparative example under ultraviolet light irradiation (UV On) and after ultraviolet light is turned off (UV Off) are shown in the figure below. Figure 1 (as shown in e in the figure).

[0079] Depend on Figure 1 It can be seen that polypropylene-based organic light-emitting materials can exhibit blue fluorescence under ultraviolet light excitation, but no afterglow appears after the ultraviolet lamp is turned off.

[0080] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A polypropylene-based organic light-emitting material, characterized in that, The composition includes polypropylene, layered silicate, and organic dye; the layered silicate is at least one selected from montmorillonite, bentonite, kaolinite, lithium montmorillonite, and halloysite; the mass percentage of the layered silicate in the polypropylene-based organic light-emitting material is 5% to 15%; the organic dye is at least one selected from β-diketone boron fluorine complex, carbazole, 1,8-naphthalenedicarboxylic anhydride, terephthalic acid, 4,4-dibromobiphenyl, and 2,4,6-trihydroxypyrimidine; the mass percentage of the organic dye in the polypropylene-based organic light-emitting material is 0.1% to 10%.

2. The polypropylene-based organic light-emitting material according to claim 1, characterized in that: The number-average molecular weight of the polypropylene is 200,000 g / mol to 600,000 g / mol.

3. A method for preparing a polypropylene-based organic light-emitting material as described in claim 1 or 2, characterized in that, The process includes the following steps: mixing polypropylene, layered silicate and organic dye for melt processing, followed by cooling and molding to obtain polypropylene-based organic light-emitting materials.

4. The preparation method according to claim 3, characterized in that: The melt processing is carried out at a temperature of 150℃ to 250℃.

5. The preparation method according to claim 3 or 4, characterized in that: The product obtained by the cooling and molding process is in the form of granules, threads, or films.

6. The application of a polypropylene-based organic light-emitting material as described in claim 1 or 2 in the fields of display, bioimaging, or anti-counterfeiting encryption.

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