Polysaccharide derivatives, methods of preparation, and organic room-temperature phosphorescent inks containing the same and methods of preparation

Abstract

The application discloses a polysaccharide derivative, a preparation method and an organic room-temperature phosphorescent ink containing the polysaccharide derivative and a preparation method, and the polysaccharide derivative has a structure as shown in formula I: wherein A1, A2 and A3 are the same or different, and are independently selected from H, -C(=O)-CH3 or an R group; and Y is selected from O or NH. The application utilizes cellulose nanocrystals to immobilize the polysaccharide derivative with an aromatic group on the surface of the cellulose nanocrystals through hydrogen bond interaction, effectively limits the movement of the molecular chain and the light-emitting group of the polysaccharide derivative, and inhibits non-radiative transition. Meanwhile, the cellulose nanocrystals with a strong hydrogen bond network can isolate oxygen, and the polysaccharide derivative can adjust the phosphorescent emission color by changing the structure of the aromatic group, so that a room-temperature phosphorescent ink with multiple colors is prepared. The room-temperature phosphorescent ink can be used for preparing a multicolor phosphorescent anti-counterfeiting label, an information storage pattern and the like through simple and easy methods such as printing and screen printing.

Description

Technical Field

[0001] This application belongs to the technical field of organic optical materials and functional coating materials, and specifically relates to a polysaccharide derivative, its preparation method, and an organic room temperature phosphorescent ink containing the derivative and its preparation method. Background Technology

[0002] Pure organic room-temperature phosphorescent materials have attracted widespread research interest due to their increasingly prominent application value in fields such as information storage, information encryption, cell imaging, and optical displays. Organic room-temperature phosphorescent coatings are composed of cellulose nanocrystals, polysaccharide derivatives, and solvents. They possess a variety of phosphorescent colors, and multi-color patterns can convey richer information. Furthermore, multi-color phosphorescence, due to its time-dependent nature and dual emission properties (fluorescence and phosphorescence), can conceal or load even richer information. However, because they are strongly dependent on the excitation wavelength or time, the phosphorescence emission wavelength of these materials is easily limited, making it difficult to achieve full coverage of the visible light spectrum. Moreover, the phosphorescence emission wavelength is not easily precisely adjusted, making the preparation of multi-color room-temperature phosphorescent materials still challenging. Summary of the Invention

[0003] The present invention aims to provide a polysaccharide derivative, a preparation method thereof, and an organic room temperature phosphorescent ink containing the derivative and a preparation method thereof. The polysaccharide derivative can control its phosphorescence emission color by changing the structure of the aromatic group, thereby obtaining room temperature phosphorescent inks of various colors.

[0004] To achieve the above objectives, according to one aspect of the present invention, a polysaccharide derivative having a structure as shown in Formula I is provided:

[0005]

[0006] Among them: A1, A2, and A3 may be the same or different, and are independently selected from H, -C(=O)-CH3 or R groups;

[0007] Y is selected from O or NH;

[0008] The R group is selected from one or more of the following structures:

[0009]

[0010] According to one embodiment of the present invention, the main chain of the polysaccharide derivative is one or more of cellulose, starch, chitosan and chitin.

[0011] Preferably, the degree of polymerization of the main chain of the polysaccharide derivative is between 100 and 5000.

[0012] More preferably, the degree of polymerization of the main chain of the polysaccharide derivative is 120-1500, for example 150, 220, 300, 400, 500, 600, 700, 800, 900, 1000.

[0013] Preferably, the polysaccharide derivative is cellulose 4-(diphenylamino)phenylbenzoate, starch (3,5-diphenylphenyl)phenylaminocarbamate, chitosan 1-pyrene phenylaminocarbamate or cellulose 4-(9-carbazole)benzoate.

[0014] Preferably, the degree of substitution of the R group in the polysaccharide is 0.01-2.00.

[0015] More preferably, the degree of substitution of the R group in the polysaccharide is 0.01-1.50, for example 0.10, 0.30, 0.55, 0.61, 0.90.

[0016] According to another aspect of the present invention, an organic room temperature phosphorescent ink is provided, comprising cellulose nanocrystals and a polysaccharide derivative having aromatic groups immobilized on its surface through hydrogen bonding interactions; said polysaccharide derivative is the polysaccharide derivative having the structure shown in Formula I.

[0017] According to one embodiment of the present invention, the cellulose nanocrystals have a diameter of 5-80 nm and a length of 100-800 nm.

[0018] Preferably, the cellulose nanocrystals have a diameter of 10-60 nm and a length of 200-600 nm.

[0019] Preferably, the mass concentration of cellulose nanocrystals in the organic room temperature phosphorescent ink is 0.05-10%, more preferably 0.1-6.91%. For example, 0.1%, 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, 3.81%, 4.0%, 4.5%, 5.0%, 5.61%, 5.63%.

[0020] Preferably, the mass concentration of the polysaccharide derivative in the organic room temperature phosphorescent ink is 0.05-10%.

[0021] Further preferably, it is 0.45-5%, more preferably 0.95-5%. For example, 0.92%, 0.93%, 0.95%, 1.6%, 2.0%, 2.56%, 3.0%, 3.5%, 4.0%, 4.5%, 5.0%.

[0022] According to another aspect of the present invention, a method for preparing a polysaccharide derivative is provided, comprising:

[0023] S1, add the polysaccharide to solvent I, heat to a certain temperature to dissolve it, and obtain a polysaccharide solution;

[0024] S2, Add reagent I to the polysaccharide solution, then heat to a certain temperature to react and obtain an intermediate;

[0025] S3, dissolve the intermediate in solvent II, add reagent II, with or without catalyst I and / or catalyst II, heat to a certain temperature to react, and obtain polysaccharide derivative;

[0026] The polysaccharide backbone is one or more of cellulose, starch, chitosan, and chitin.

[0027] The reagent I is selected from at least one of acyl chlorides, isocyanates, or carboxylic acids containing a bromoaromatic group;

[0028] The reagent II is selected from boric acid containing aromatic groups; the solvent I is selected from imidazole ionic liquids;

[0029] Solvent II is selected from one or more of sulfone solvents, amide solvents, and furan solvents.

[0030] According to one embodiment of the present invention, the polysaccharide solution obtained by dissolving the polysaccharide in solvent I has a mass percentage concentration of 1-15%, preferably 3-10%, for example 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%.

[0031] Preferably, the dissolution temperature of the polysaccharide in step S1 is 30-120℃, more preferably 80℃-130℃, for example, 80℃, 90℃, 100℃, 110℃, 120℃.

[0032] Preferably, the molar ratio of the polysaccharide to reagent I is 1:0.5-1:10; more preferably, it is 1:1-1:5; for example, 1:1, 1:2, 1:3, 1:4, 1:5.

[0033] According to one embodiment of the present invention, reagent I is one or more of 4-bromobenzoyl chloride, 4-bromophenyl isocyanate, 4-bromobenzoic acid, 3-bromobenzoyl chloride, 3-bromophenyl isocyanate and 3-bromobenzoic acid.

[0034] Preferably, reagent II is one or more of 4-(diphenylamino)phenylboronic acid, (3,5-diphenylphenyl)boronic acid, 4-(9-carbazolyl)phenylboronic acid, 4-(diphenylamino)phenylboronic acid, and 1-pyreneboronic acid.

[0035] Preferably, the reaction temperature in step S2 is 30-120℃; more preferably 70-120℃. For example, 70℃, 75℃, 80℃, 85℃, 90℃, 95℃, 100℃, 105℃, 110℃, 115℃, 120℃.

[0036] Preferably, the reaction time in step S2 is 1-12 hours, more preferably 3-12 hours, and even more preferably 6-12 hours.

[0037] According to one embodiment of the present invention, the intermediate has a mass percentage concentration of 1-15% in solvent II, preferably 3-10%, for example 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%.

[0038] Preferably, catalyst I is selected from palladium-based catalysts; more preferably, catalyst I is selected from at least one of tetra(triphenylphosphine)palladium, bis(triphenylphosphine)palladium chloride, and bis(triphenylphosphine)palladium dichloride.

[0039] Preferably, catalyst II is selected from carbonates and / or bicarbonates. More preferably, catalyst II is selected from one or more of potassium carbonate, sodium carbonate, and potassium bicarbonate.

[0040] Preferably, the molar ratio of the intermediate to catalyst I is 1:0.0001-1:5, and more preferably 1:0.001-1:0.5.

[0041] Preferably, the molar ratio of the intermediate to catalyst II is 1:0.01-1:5, more preferably 1:0.1-1:0.5;

[0042] Preferably, the molar ratio of the intermediate to reagent II is 1:0.01-1:10, and more preferably 1:0.1-1:5.

[0043] Preferably, the reaction temperature in step S3 is 30-120℃ and the reaction time is 6-36 hours; preferably, the reaction temperature is 60℃-120℃ and the reaction time is 12-24 hours.

[0044] Preferably, the reaction further includes adding a precipitant to the reaction system after reaction step S3, followed by washing and drying; the precipitant is selected from one or more of water, methanol, ethanol, isopropanol, and methanol.

[0045] According to one embodiment of the present invention, the imidazole ionic liquid is a 1-ethyl-3-methylimidazolium chloride ionic liquid, a 1-ethyl-3-methylimidazolium bromide ionic liquid, a 1-allyl-3-methylimidazolium chloride ionic liquid, a 1-allyl-3-methylimidazolium bromide ionic liquid, a 1-butyl-3-methylimidazolium chloride ionic liquid, a 1-butyl-3-methylimidazolium bromide ionic liquid, a 1-ethyl-3-methylimidazolium acetate ionic liquid, or a 1-allyl-3-methylimidazolium acetate ionic liquid. One or more of the following: ionic liquid, 1-butyl-3-methylimidazolium acetate ionic liquid, N-ethylpyridine chloride ionic liquid, N-ethylpyridine bromide ionic liquid, 1,3-dimethylimidazolium dimethyl phosphate ionic liquid, 1-ethyl-3-methylimidazolium diethyl phosphate ionic liquid, 3-methylimidazolium carboxylate ionic liquid, N-methylpyridine carboxylate ionic liquid, 1-ethyl-3-methylimidazolium carboxylate ionic liquid, and 1-butyl-3-methylimidazolium carboxylate ionic liquid.

[0046] Preferably, solvent II is selected from one or more of dimethyl sulfoxide, N,N-dimethylformamide and N,N-dimethylacetamide.

[0047] According to another aspect of the present invention, a method for preparing an organic room temperature phosphorescent ink is also provided, comprising adding a polysaccharide derivative and cellulose nanocrystals to water or an organic solvent, and sonicating to obtain an organic room temperature phosphorescent ink; wherein the polysaccharide derivative is a polysaccharide derivative with the structure shown in Formula I above; or a polysaccharide derivative prepared by the above method.

[0048] Preferably, the organic solvent is selected from at least one of dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), chloroform, dichloromethane, 1,2-dichloroethane, acetone, tetrahydrofuran (THF), N-methylpyrrolidone, pyridine, ethanol, methanol, isopropanol, ethyl acetate, butyl acetate, toluene, and methyl ethyl ketone.

[0049] The beneficial effects of this invention are:

[0050] This invention utilizes cellulose nanocrystals to immobilize polysaccharide derivatives with aromatic groups on their surface through hydrogen bonding interactions. This effectively restricts the movement of the polysaccharide derivative molecular chains and luminescent groups, suppressing non-radiative transitions. Simultaneously, the cellulose nanocrystals, with their strong hydrogen bond network, can isolate oxygen. By modifying the structure of the aromatic groups, the phosphorescence emission color of the polysaccharide derivatives can be controlled, thus producing room-temperature phosphorescent inks of various colors. These inks can be easily prepared using simple methods such as printing and screen printing to create multi-color phosphorescent anti-counterfeiting labels, information storage patterns, etc. Attached Figure Description

[0051] Figure 1The image shows the hydrogen nuclear magnetic resonance spectrum of the cellulose derivative prepared in Example 1.

[0052] Figure 2 The images show optical photographs (left), ultraviolet light photographs (middle), and transmission electron microscope photographs (right) of the phosphorescent ink prepared in Example 1.

[0053] Figure 3 The images show the fluorescence and phosphorescence of the phosphorescent ink prepared in Example 1 after drying.

[0054] Figure 4 The fluorescence and phosphorescence spectra of the phosphorescent ink prepared in Example 2 are shown.

[0055] Figure 5 Phosphorescent photograph of the phosphorescent ink prepared in Example 3.

[0056] Figure 6 The phosphorescent pattern printed with the phosphorescent ink prepared in Example 4 is shown in the fluorescence and phosphorescence images with a 365nm ultraviolet lamp turned on and off. Detailed Implementation

[0057] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be emphasized that the specific embodiments described herein are only for better illustrating the invention and represent some, not all, embodiments, and therefore are not intended to limit the invention. Furthermore, the technical features involved in the embodiments of the invention described below can be combined with each other as long as they do not conflict with each other.

[0058] Example 1

[0059] Preparation of polysaccharide derivatives:

[0060] 6 g of cellulose was dissolved in 114 g of the ionic liquid 1-allyl-3-methylimidazolium chloride (AmimCl), and 24.88 g of reagent I 4-bromobenzoyl chloride was added. The mixture was heated to 70 °C and reacted for 3 h. After the reaction was completed, ethanol was added to the reaction system to remove unreacted 4-bromobenzoyl chloride. The reaction solution was then precipitated in a mixed solvent of ethanol / water (v / v = 1 / 1). The precipitate was filtered, washed with ethanol, and filtered again. This process was repeated at least three times. Finally, the sample was washed with water and filtered once more. The sample was then dried in a vacuum oven for at least 24 h to obtain the intermediate cellulose 4-bromobenzoate with a degree of substitution of 1.42.

[0061] Take 8.4g of the intermediate cellulose 4-bromobenzoate prepared above, dissolve it in 40mL of solvent II, oven-dry tetrahydrofuran (THF), add 50mg of catalyst I, tetra(triphenylphosphine)palladium, 100mg of catalyst II, K2CO3 and 1.0g of reagent II, 4-(diphenylamino)phenylboronic acid, and react at 60℃ for 24h.

[0062] After the reaction was completed, the reaction mixture was precipitated in a mixed solvent of ethanol / water (v / v = 1 / 1). The precipitate was filtered, ethanol was added and washed again, and the mixture was filtered again. This process was repeated three or more times. The sample was then washed with water and filtered again. Finally, the sample was placed in a vacuum oven and dried for more than 24 hours to obtain the polysaccharide derivative cellulose 4-(diphenylamino)phenylbenzoate.

[0063] The degree of substitution of 4-(diphenylamino)phenylbenzoate in the cellulose derivative is 0.90, and its proton NMR spectrum is shown below. Figure 1 As shown (test instrument: Bruker AV400 nuclear magnetic resonance spectrometer, solvent: deuterated dimethyl sulfoxide (DMSO-d6)).

[0064] 0.2 g of the above-mentioned polysaccharide derivative, 0.8 g of cellulose nanocrystals (20 nm in diameter and 500 nm in length), and 20 g of the organic solvent N,N-dimethylformamide (DMF) were mixed and sonicated for 10 min to obtain an organic room-temperature phosphorescent ink. The polysaccharide derivative had a mass concentration of 0.95%, and the cellulose nanocrystals had a mass concentration of 3.81%.

[0065] Figure 2 Images (a), (b), and (c) are optical photographs (left), ultraviolet light photographs (middle), and transmission electron microscope photographs (right) of the phosphorescent ink prepared in Example 1, respectively. Camera: Sony α7, excitation wavelength: 365 nm. Transmission electron microscope: JEOL JSM-2200FS, accelerating voltage: 200 kV.

[0066] from Figure 2 As can be seen from the above, the phosphorescent ink prepared in Example 1 maintains the nanoscale size of cellulose nanocrystals and can be used as a nano-phosphorescent ink material.

[0067] After drying, the phosphorescent ink emits cyan fluorescence under 365nm ultraviolet light and yellow phosphorescence for more than 4 seconds after the ultraviolet light is turned off. Figure 3 As shown (camera: Sony α7, excitation wavelength: 365nm).

[0068] Example 2

[0069] 2 g of starch was dissolved in 48.0 g of 1-butyl-3-methylimidazolium chloride ionic liquid (BmimCl) / DMF (mass ratio 4:1), and 5.8 g of reagent I 4-bromophenyl isocyanate was added. The mixture was heated to 70 °C and reacted for 2 h. After the reaction was completed, ethanol was added to the reaction system to remove unreacted 4-bromophenyl isocyanate. The reaction solution was then precipitated in a mixed solvent of ethanol / water (v / v = 1 / 1). The precipitate was filtered, washed with ethanol, and filtered again. This process was repeated at least three times. Finally, the sample was washed with water and filtered once more. The sample was then dried in a vacuum oven for at least 24 h to obtain the intermediate product starch 4-bromophenylaminocarbamate with a degree of substitution of 0.92.

[0070] Take 1g of the intermediate product starch 4-bromophenylcarbamate prepared above, dissolve it in 15mL of solvent II, oven-dry tetrahydrofuran (THF), add 15mg of catalyst I, tetrakis(triphenylphosphine)palladium, 60mg of catalyst II, K₂CO₃, and 2g of reagent II, (3,5-diphenylphenyl)boric acid, and react at 60℃ for 24h. After the reaction is complete, precipitate the reaction mixture in a mixed solvent of ethanol / water (v / v = 1 / 1), filter the precipitate, add ethanol and continue washing, filter again, repeat the operation more than three times, finally wash the sample with water and filter once more, place the sample in a vacuum oven and dry for more than 24h to obtain starch (3,5-diphenylphenyl)phenylcarbamate. The degree of substitution of the polysaccharide derivative starch (3,5-diphenylphenyl)phenylcarbamate is 0.54.

[0071] 1 g of starch 4-bromophenylcarbamate was dissolved in 15 mL of solvent II, oven-dry tetrahydrofuran (THF). 15 mg of catalyst I, tetrakis(triphenylphosphine)palladium, 60 mg of catalyst II, K₂CO₃, and 3.5 g of reagent II, 4-(9-carbazole)phenylboronic acid, were added. The reaction was carried out at 60 °C for 24 h. After the reaction, the reaction mixture was precipitated in a mixed solvent of ethanol / water (v / v = 1 / 1). The precipitate was filtered, washed with ethanol, and filtered again. This process was repeated at least three times. Finally, the sample was washed with water and filtered once more. The sample was then dried in a vacuum oven for at least 24 h to obtain starch 4-(9-carbazole)phenylcarbamate. The degree of substitution of the polysaccharide derivative starch 4-(9-carbazole)phenylcarbamate was 0.61.

[0072] 0.2 g of starch (3,5-diphenylphenyl)phenylcarbamate, 0.3 g of starch 4-(9-carbazolyl)phenylcarbamate, 0.8 g of cellulose nanocrystals, and 30 g of N,N-dimethylformamide (DMF) were mixed and sonicated for 10 min to obtain an organic room-temperature phosphorescent ink. The polysaccharide derivative in the organic room-temperature phosphorescent ink had a mass concentration of 1.60%, and the cellulose nanocrystals had a mass concentration of 2.56%.

[0073] The fluorescence spectrum and phosphorescence spectrum of phosphorescent ink are as follows: Figure 4 As shown (test instrument: HITACHI F-7000 spectrophotometer, excitation wavelength 365nm). From Figure 4 It can be seen that the fluorescence emission wavelength of the phosphorescent ink is 460nm, and the phosphorescence emission wavelength is 525nm.

[0074] After drying, the phosphorescent ink emits cyan fluorescence under 365nm ultraviolet light and green phosphorescence when the ultraviolet light is turned off.

[0075] Example 3

[0076] 2 g of chitosan was dissolved in 48 g of 1-ethyl-3-methylimidazolium acetate ionic liquid (EmimAc), and 8.0 g of reagent I, 4-bromophenyl isocyanate, was added. The mixture was heated to 70 °C and reacted for 2 h. After the reaction was complete, ethanol was added to the reaction system to remove unreacted 4-bromophenyl isocyanate. The reaction solution was then precipitated in a mixed solvent of ethanol / water (v / v = 1 / 1). The precipitate was filtered, washed with ethanol, and filtered again. This process was repeated at least three times. Finally, the sample was washed with water and filtered once more. The sample was then dried in a vacuum oven for at least 24 h to obtain the intermediate product chitosan 4-bromophenylcarbamate with a degree of substitution of 1.20.

[0077] 1 g of chitosan 4-bromophenylcarbamate was dissolved in 15 mL of oven-dry tetrahydrofuran (THF). 15 mg of tetrakis(triphenylphosphine)palladium, 60 mg of K₂CO₃, and 2 g of 2-naphthoboric acid were added, and the mixture was reacted at 60 °C for 24 h. After the reaction, the reaction mixture was precipitated in a mixed solvent of ethanol / water (v / v = 1 / 1). The precipitate was filtered, washed with ethanol, and filtered again. This process was repeated at least three times. Finally, the sample was washed with water and filtered once more. The sample was then dried in a vacuum oven for at least 24 h to obtain chitosan 2-naphthophenylcarbamate. The degree of substitution of chitosan 2-naphthophenylcarbamate was 0.87.

[0078] 1 g of chitosan 4-bromophenylcarbamate was dissolved in 15 mL of oven-dry tetrahydrofuran (THF), and 15 mg of tetra(triphenylphosphine)palladium, 60 mg of K₂CO₃, and 3.5 g of 1-pyreneboronic acid were added. The mixture was reacted at 60 °C for 24 h. After the reaction was completed, the reaction mixture was precipitated in a mixed solvent of ethanol / water (v / v = 1 / 1). The precipitate was filtered, washed with ethanol, and filtered again. This process was repeated at least three times. Finally, the sample was washed with water and filtered once more. The sample was then dried in a vacuum oven for at least 24 h to obtain chitosan 1-pyrenephenylcarbamate. The degree of substitution of chitosan 1-pyrenephenylcarbamate was 0.61.

[0079] Chitosan 2-naphthylphenylcarbamate and chitosan 1-pyrenephenylcarbamate were mixed at different mass ratios (total weight 0.5 g), then mixed with 6 g of cellulose nanocrystals and 100 g of N,N-dimethylformamide (DMF), and sonicated for 10 min to obtain an organic room-temperature phosphorescent ink. The polysaccharide derivative in the organic room-temperature phosphorescent ink had a mass concentration of 0.45%, and the cellulose nanocrystals had a mass concentration of 5.63%.

[0080] The phosphorescence of phosphorescent ink is as follows Figure 5 As shown (camera: Sony α7, excitation wavelength: 365nm).

[0081] Example 4

[0082] 6 g of cellulose was dissolved in 114 g of the ionic liquid 1-allyl-3-methylimidazolium chloride (AmimCl), and 24.88 g of reagent I 4-bromobenzoyl chloride was added. The mixture was heated to 70 °C and reacted for 3 h. After the reaction was completed, ethanol was added to the reaction system to remove unreacted 4-bromobenzoyl chloride. The reaction solution was then precipitated in a mixed solvent of ethanol / water (v / v = 1 / 1). The precipitate was filtered, washed with ethanol, and filtered again. This process was repeated at least three times. Finally, the sample was washed with water and filtered once more. The sample was then dried in a vacuum oven for at least 24 h to obtain the intermediate product cellulose 4-bromobenzoate with a degree of substitution of 1.42.

[0083] 4.2 g of cellulose 4-bromobenzoate was dissolved in 40 mL of solvent II, oven-dry tetrahydrofuran (THF). 25 mg of catalyst I, tetratetra(triphenylphosphine)palladium, 50 mg of catalyst II, K₂CO₃, and 0.5 g of reagent II, 4-(diphenylamino)phenylboronic acid, were added. The reaction was carried out at 60 °C for 24 h. After the reaction, the reaction mixture was precipitated in a mixed solvent of ethanol / water (v / v = 1 / 1). The precipitate was filtered, washed with ethanol, and filtered again. This process was repeated at least three times. Finally, the sample was washed with water and filtered once more. The sample was then dried in a vacuum oven for at least 24 h to obtain cellulose 4-(diphenylamino)phenylbenzoate. The degree of substitution of 4-(diphenylamino)phenyl in the cellulose derivative was 0.90.

[0084] 1 g of cellulose 4-bromobenzoate was dissolved in 15 mL of solvent II, oven-dry tetrahydrofuran (THF). 15 mg of catalyst I, tetrakis(triphenylphosphine)palladium, 60 mg of catalyst II, K₂CO₃, and 3.5 g of reagent II, 1-pyreneboric acid, were added. The mixture was reacted at 60 °C for 24 h. After the reaction, the reaction mixture was precipitated in a mixed solvent of ethanol / water (v / v = 1 / 1). The precipitate was filtered, washed with ethanol, and filtered again. This process was repeated at least three times. Finally, the sample was washed with water and filtered once more. The sample was then dried in a vacuum oven for at least 24 h to obtain cellulose 1-pyrenebenzoate. The degree of substitution of cellulose 1-pyrenebenzoate was 0.55.

[0085] 1 g of cellulose 4-bromobenzoate was dissolved in 15 mL of solvent II, oven-dry tetrahydrofuran (THF). 15 mg of catalyst I, tetrakis(triphenylphosphine)palladium, 60 mg of catalyst II, K₂CO₃, and 3.5 g of reagent II, 4-(9-carbazole)phenylboronic acid, were added. The reaction mixture was reacted at 60 °C for 24 h. After the reaction, the reaction mixture was precipitated in a mixed solvent of ethanol / water (v / v = 1 / 1). The precipitate was filtered, washed with ethanol, and filtered again. This process was repeated at least three times. Finally, the sample was washed with water and filtered once more. The sample was then dried in a vacuum oven for at least 24 h to obtain cellulose 4-(9-carbazole)benzoate. The degree of substitution of cellulose 4-(9-carbazole)benzoate was 0.39.

[0086] 0.2 g of cellulose 4-(diphenylamino)phenylbenzoate, 0.8 g of cellulose nanocrystals, and 20 g of N,N-dimethylformamide (DMF) were mixed and sonicated for 10 min to obtain a yellow phosphorescent ink. The polysaccharide derivative had a mass concentration of 0.95%, and the cellulose nanocrystals had a mass concentration of 3.81%.

[0087] 0.2 g of cellulose 4-(9-carbazole)benzoate, 1.5 g of cellulose nanocrystals, and 20 g of N,N-dimethylformamide (DMF) were mixed and sonicated for 10 min to obtain a green phosphorescent ink. The polysaccharide derivative had a mass concentration of 0.92%, and the cellulose nanocrystals had a mass concentration of 6.91%.

[0088] 0.2 g of cellulose 1-pyrene benzoate, 1.2 g of cellulose nanocrystals, and 20 g of N,N-dimethylformamide (DMF) were mixed and sonicated for 10 min to obtain a red phosphorescent ink. The polysaccharide derivative had a mass concentration of 0.93%, and the cellulose nanocrystals had a mass concentration of 5.61%.

[0089] The above three inks were used to print color patterns using an inkjet printer. Fluorescent and phosphorescent photographs taken with and without a 365nm ultraviolet lamp were then produced. Figure 6As shown (camera: Sony α7, excitation wavelength: 365nm).

[0090] Finally, it should be noted that the above specific embodiments are only used to illustrate the technical solutions of the present invention and not to limit it. Although the present invention has been described in detail with reference to examples, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all such modifications or substitutions should be covered within the scope of the claims of the present invention.

Claims

1. An organic room temperature phosphorescent ink, characterized in that, This includes cellulose nanocrystals and polysaccharide derivatives immobilized on their surface via hydrogen bonding interactions and possessing aromatic groups; the polysaccharide derivatives have a structure as shown in Formula I: Formula I in: A1, A2, and A3 may be the same or different, and are independently selected from H, -C(=O)-CH3, or R groups; Y is selected from O or NH; The R group is selected from one or more of the following structures: 。 2. The organic room temperature phosphorescent ink according to claim 1, characterized in that, The main chain of the polysaccharide derivative is one or more of cellulose, starch, chitosan and chitin.

3. The organic room temperature phosphorescent ink according to claim 1, characterized in that, The degree of polymerization of the main chain of the polysaccharide derivative is between 100 and 5000.

4. The organic room temperature phosphorescent ink according to claim 3, characterized in that, The degree of polymerization of the main chain of the polysaccharide derivative is 120-1500.

5. The organic room temperature phosphorescent ink according to claim 4, characterized in that, The degree of polymerization of the main chain of the polysaccharide derivative is 150, 220, 300, 400, 500, 600, 700, 800, 900, or 1000.

6. The organic room temperature phosphorescent ink according to claim 1, characterized in that, The polysaccharide derivative is cellulose 4-(diphenylamino)phenylbenzoate, starch (3,5-diphenylphenyl)phenylaminobenzoate, chitosan 1-pyrene phenylaminobenzoate or cellulose 4-(9-carbazole)benzoate.

7. The organic room temperature phosphorescent ink according to claim 1, characterized in that, The degree of substitution of the R group in the polysaccharide is 0.01-2.

00.

8. The organic room temperature phosphorescent ink according to claim 7, characterized in that, The degree of substitution of the R group in the polysaccharide is 0.01-1.

50.

9. The organic room temperature phosphorescent ink according to claim 8, characterized in that, The degree of substitution of the R group in the polysaccharide is 0.10, 0.30, 0.55, 0.61, and 0.

90.

10. The organic room temperature phosphorescent ink according to claim 1, characterized in that, The cellulose nanocrystals have a diameter of 5-80 nm and a length of 100-800 nm.

11. The organic room temperature phosphorescent ink according to claim 10, characterized in that, The cellulose nanocrystals have a diameter of 10-60 nm and a length of 200-600 nm.

12. The organic room temperature phosphorescent ink according to claim 1, characterized in that, The organic room temperature phosphorescent ink has a cellulose nanocrystal mass concentration of 0.05-10%.

13. The organic room temperature phosphorescent ink according to claim 12, characterized in that, The organic room temperature phosphorescent ink has a cellulose nanocrystal mass concentration of 0.1-6.91%.

14. The organic room temperature phosphorescent ink according to claim 13, characterized in that, The mass concentration of cellulose nanocrystals in the organic room temperature phosphorescent ink is 0.1%, 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, 3.81%, 4.0%, 4.5%, 5.0%, 5.61%, and 5.63%.

15. The organic room temperature phosphorescent ink according to claim 1, characterized in that, The mass concentration of polysaccharide derivatives in the organic room temperature phosphorescent ink is 0.05-10%.

16. The organic room temperature phosphorescent ink according to claim 15, characterized in that, The mass concentration of polysaccharide derivatives in the organic room temperature phosphorescent ink is 0.45-5%.

17. The organic room temperature phosphorescent ink according to claim 16, characterized in that, The mass concentration of polysaccharide derivatives in the organic room temperature phosphorescent ink is 0.95-5%.

18. The organic room temperature phosphorescent ink according to claim 16, characterized in that, The mass concentrations of polysaccharide derivatives in the organic room temperature phosphorescent ink are 0.92%, 0.93%, 0.95%, 1.6%, 2.0%, 2.56%, 3.0%, 3.5%, 4.0%, 4.5%, and 5.0%.

19. A method for preparing an organic room temperature phosphorescent ink, characterized in that, The method includes adding polysaccharide derivatives and cellulose nanocrystals to water or an organic solvent, followed by ultrasonication to obtain an organic room temperature phosphorescent ink; wherein the polysaccharide derivative is a polysaccharide derivative having the structure shown in Formula I.

20. The preparation method according to claim 19, characterized in that, The organic solvent is selected from at least one of dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, chloroform, dichloromethane, 1,2-dichloroethane, acetone, tetrahydrofuran, N-methylpyrrolidone, pyridine, ethanol, methanol, isopropanol, ethyl acetate, butyl acetate, toluene, and methyl ethyl ketone.

21. The preparation method according to claim 19, characterized in that, The preparation method of the polysaccharide derivative includes: S1, add the polysaccharide to solvent I, heat to a certain temperature to dissolve it, and obtain a polysaccharide solution; S2, Add reagent I to the polysaccharide solution, then heat to a certain temperature to react and obtain an intermediate; S3, dissolve the intermediate in solvent II, add reagent II, with or without catalyst I and / or catalyst II, heat to a certain temperature to carry out the reaction, and obtain the polysaccharide derivative; The polysaccharide backbone is one or more of cellulose, starch, chitosan, and chitin. The reagent I is selected from at least one of acyl chlorides, isocyanates, or carboxylic acids containing a bromoaromatic group; The reagent II is selected from boric acids containing aromatic groups; Solvent I is selected from imidazole ionic liquids; Solvent II is selected from one or more of sulfone solvents, amide solvents, and furan solvents.

22. The preparation method according to claim 21, characterized in that, The polysaccharide solution obtained by dissolving the polysaccharide in solvent I has a mass percentage concentration of 1-15%.

23. The preparation method according to claim 22, characterized in that, The polysaccharide solution obtained by dissolving the polysaccharide in solvent I has a mass percentage concentration of 3-10%.

24. The preparation method according to claim 23, characterized in that, The polysaccharide solutions obtained by dissolving the polysaccharides in solvent I have a mass percentage concentration of 3%, 4%, 5%, 6%, 7%, 8%, 9%, and 10%.

25. The preparation method according to claim 21, characterized in that, The dissolution temperature of the polysaccharide in step S1 is 30-120℃.

26. The preparation method according to claim 25, characterized in that, The dissolution temperature of the polysaccharide in step S1 is 80℃-130℃.

27. The preparation method according to claim 26, characterized in that, The dissolution temperature of the polysaccharide in step S1 is 80℃, 90℃, 100℃, 110℃, and 120℃.

28. The preparation method according to claim 21, characterized in that, The molar ratio of the polysaccharide to reagent I is 1:0.5-1:

10.

29. The preparation method according to claim 28, characterized in that, The molar ratio of the polysaccharide to reagent I is 1:1 to 1:

5.

30. The preparation method according to claim 29, characterized in that, The molar ratio of the polysaccharide to reagent I is 1:1, 1:2, 1:3, 1:4 or 1:

5.

31. The preparation method according to claim 21, characterized in that, The reagent I is one or more of 4-bromobenzoyl chloride, 4-bromophenyl isocyanate, 4-bromobenzoic acid, 3-bromobenzoyl chloride, 3-bromophenyl isocyanate and 3-bromobenzoic acid.

32. The preparation method according to claim 31, characterized in that, The reagent II is one or more of 4-(diphenylamino)phenylboronic acid, (3,5-diphenylphenyl)boronic acid, 4-(9-carbazolyl)phenylboronic acid, 4-(diphenylamino)phenylboronic acid, and 1-pyreneboronic acid.

33. The preparation method according to claim 21, characterized in that, The reaction temperature in step S2 is 30-120℃.

34. The preparation method according to claim 33, characterized in that, The reaction temperature in step S2 is 70-120℃.

35. The preparation method according to claim 34, characterized in that, The reaction temperature in step S2 is 70℃, 75℃, 80℃, 85℃, 90℃, 95℃, 100℃, 105℃, 110℃, 115℃, and 120℃.

36. The preparation method according to claim 21, characterized in that, The reaction time in step S2 is 1-12 hours.

37. The preparation method according to claim 36, characterized in that, The reaction time in step S2 is 3-12 hours.

38. The preparation method according to claim 21, characterized in that, The intermediate has a mass percentage concentration of 1-15% in solvent II.

39. The preparation method according to claim 38, characterized in that, The intermediate has a mass percentage concentration of 3-10% in solvent II.

40. The preparation method according to claim 39, characterized in that, The intermediate has a mass percentage concentration of 3%, 4%, 5%, 6%, 7%, 8%, 9%, and 10% in solvent II.

41. The preparation method according to claim 21, characterized in that, Catalyst I is selected from palladium-based catalysts; catalyst II is selected from carbonates and / or bicarbonates.

42. The preparation method according to claim 41, characterized in that, Catalyst I is selected from at least one of tetra(triphenylphosphine)palladium, bis(triphenylphosphine)palladium chloride, and bis(triphenylphosphine)palladium dichloride; catalyst II is selected from one or more of potassium carbonate, sodium carbonate, and potassium bicarbonate.

43. The preparation method according to claim 21, characterized in that, The molar ratio of the intermediate to catalyst I is 1:0.0001-1:

5.

44. The preparation method according to claim 43, characterized in that, The molar ratio of the intermediate to catalyst I is 1:0.001-1:0.

5.

45. The preparation method according to claim 21, characterized in that, The molar ratio of the intermediate to catalyst II is 1:0.01-1:

5.

46. ​​The preparation method according to claim 45, characterized in that, The molar ratio of the intermediate to catalyst II is 1:0.1 to 1:0.

5.

47. The preparation method according to claim 21, characterized in that, The molar ratio of the intermediate to reagent II is 1:0.01-1:

10.

48. The preparation method according to claim 47, characterized in that, The molar ratio of the intermediate to reagent II is 1:0.1-1:

5.

49. The preparation method according to claim 21, characterized in that, The reaction temperature in step S3 is 30-120℃, and the reaction time is 6-36 hours.

50. The preparation method according to claim 49, characterized in that, The reaction temperature in step S3 is 60℃-120℃, and the reaction time is 12-24 hours.

51. The preparation method according to claim 21, characterized in that, It also includes the steps of adding a precipitant to the reaction system after reaction step S3, followed by washing and drying; The precipitant is selected from one or more of water, methanol, ethanol, isopropanol, and methanol.

52. The preparation method according to claim 21, characterized in that, The imidazole ionic liquid is one or more of the following: 1-ethyl-3-methylimidazolium chloride ionic liquid, 1-ethyl-3-methylimidazolium bromide ionic liquid, 1-allyl-3-methylimidazolium chloride ionic liquid, 1-allyl-3-methylimidazolium bromide ionic liquid, 1-butyl-3-methylimidazolium chloride ionic liquid, 1-butyl-3-methylimidazolium bromide ionic liquid, 1-ethyl-3-methylimidazolium acetate ionic liquid, 1-allyl-3-methylimidazolium acetate ionic liquid, 1-butyl-3-methylimidazolium acetate ionic liquid, N-ethylpyridine chloride ionic liquid, N-ethylpyridine bromide ionic liquid, 1,3-dimethylimidazolium dimethyl phosphate ionic liquid, 1-ethyl-3-methylimidazolium diethyl phosphate ionic liquid, 3-methylimidazolium carboxylate ionic liquid, N-methylpyridine carboxylate ionic liquid, 1-ethyl-3-methylimidazolium carboxylate ionic liquid, and 1-butyl-3-methylimidazolium carboxylate ionic liquid.

53. The preparation method according to claim 21, characterized in that, Solvent II is selected from one or more of dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, and tetrahydrofuran.

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