A method for preparing long-afterglow multicolor phosphorescent textiles using arylboronic acid derivatives

Abstract

This invention discloses a method for preparing long-afterglow multicolor phosphorescent textiles using arylboronic acid derivatives: arylboronic acid, an alkali, an organic solvent, and water are mixed to prepare different types of arylboronic acid working solutions, which are then ultrasonically vibrated; fabric is placed in the arylboronic acid working solutions and dyed and fixed in a dyeing machine, then removed and allowed to cool naturally; the fabric is then removed, washed, and dried in an oven to obtain the finished phosphorescent textile, which is then sealed and dried. After the above treatment, arylboronic acid and its derivatives can react with fiber macromolecules in the aqueous phase to form covalent bonds, thus obtaining high-fastness long-afterglow phosphorescent textiles. By adjusting the types of arylboronic acid and its derivatives, multicolor phosphorescent textiles can be prepared, which can be applied in fields such as anti-counterfeiting and marking. This invention uses inexpensive and readily available raw materials to prepare multicolor phosphorescent textiles, resulting in low cost and minimal environmental impact, and can be applied to large-scale batch processing.

Description

Technical Field

[0001] This invention belongs to the fields of textile printing and dyeing, and luminescent anti-counterfeiting, and specifically relates to a method for preparing long-afterglow multicolor phosphorescent textiles using arylboronic acid derivatives. Background Technology

[0002] The long lifespan of room-temperature phosphorescent (RTP) materials makes them promising for applications in optoelectronics, sensing, bioimaging, and advanced security and anti-counterfeiting. However, the synthesis of traditional petroleum-based RTP materials is limited by the expensive and toxic organic solvents used, the stringent reaction conditions, and the difficulty in degrading petroleum-based materials. Polysaccharide-based materials, on the other hand, are green, environmentally friendly, and utilize renewable and biodegradable raw materials, making them an important direction for the development of the international new materials industry.

[0003] Currently, there are many materials with polysaccharide-based room-temperature phosphorescence, such as cellulose, lignin, starch, and sodium alginate, which have been extensively reported. However, these materials suffer from drawbacks such as microcrystallization, harsh reaction conditions, and short luminescence lifetimes, significantly increasing the difficulty of preparation and hindering the requirements of green environmental protection and sustainable development. Therefore, developing an environmentally friendly, biodegradable, and tunable multicolor phosphorescent textile is of significant practical importance. Arylboronic acid and its derivatives, as phosphorescent molecules, contain benzene rings with varying degrees of conjugation, enabling the prepared phosphorescent fabrics to possess long-afterglow, multicolor, and tunable RTP emission characteristics. Furthermore, they exhibit stability, low toxicity, and environmental friendliness, making them valuable in the research and application of organic small-molecule room-temperature phosphorescent materials. Cellulose fibers possess intra-chain hydrogen bonds, inter-chain hydrogen bonds, hydrogen bonds in crystalline and amorphous regions, and non-centrosymmetric hydrogen bonds, which endow cellulose chains with properties such as stability, rigidity, and reactive sites. A large number of free hydrogen bonds are combined with phosphor molecules by boron-oxygen (BO) covalent bonds, promoting intersystem crossing (ISC), enhancing π-π interactions, and facilitating rigid stacking structures, thereby increasing phosphorescence lifetime and realizing long-afterglow multicolor phosphorescent textiles. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to provide a method for preparing long-afterglow multicolor phosphorescent textiles using arylboronic acid derivatives.

[0005] To address the above problems, this invention provides a method for preparing long-afterglow multicolor phosphorescent textiles using arylboronic acid derivatives, comprising the following steps:

[0006] Step 1): Arylboronic acid, alkali, organic solvent and water are mixed to prepare different types of arylboronic acid working solutions and then ultrasonically vibrated.

[0007] Step 2): Place the fabric in the arylboric acid working solution, complete the dyeing and color fixing in the dyeing machine, and then remove it to cool naturally;

[0008] Step 3): Take out the fabric, wash it, and then place it in an oven to dry, obtaining the finished phosphorescent fabric. Seal and dry it.

[0009] Preferably, in step 1), the arylboronic acid is at least one of 2-triphenylenylboronic acid (TP-B), phenanthrene-9-boronic acid (Phe9-B), and 1-pyreneboronic acid (1Py-B); when the arylboronic acid is 2-triphenylenylboronic acid (TP-B), its amount (owf) is 0.5-5%; when the arylboronic acid is phenanthrene-9-boronic acid (Phe9-B), its amount (owf) is 0.5-4%; and when the arylboronic acid is 1-pyreneboronic acid (1Py-B), its amount (owf) is 0.5-3%.

[0010] Preferably, in step 1), the alkali agent is at least one of ammonia, sodium carbonate, sodium bicarbonate, potassium carbonate, and cesium carbonate, and the dosage is 5-40 g / L.

[0011] Preferably, in step 1), the organic solvent is at least one of ethanol, methanol, acetone, and tetrahydrofuran.

[0012] Preferably, in step 1), the volume ratio of organic solvent to water is 1:9-1:4, and the total amount of organic solvent and water used is 5-20 times the weight of the fabric in step 2).

[0013] Preferably, in step 1), the ultrasonic oscillation time is 30-60 minutes.

[0014] Preferably, in step 2), the fabric includes at least one of cotton, viscose fiber, wool, silk, and polyamide fiber; the fabric is a pre-treated fabric that has undergone degreasing and impurity removal.

[0015] Preferably, in step 2), the dyeing and fixing temperature is 80-85℃ and the time is 20-60min.

[0016] Preferably, in step 3), the washing method is to rinse with deionized water 4-5 times.

[0017] Preferably, in step 3), the drying temperature is 70-105℃ and the time is 30-60min.

[0018] The BO bond bonding mechanism in this invention is as follows: First, under alkaline conditions (pH≥10), the arylboronic acid derivative phosphor molecule provides an empty orbital and coordinates with the oxygen atom on the OH- group by providing a lone pair of electrons, forming an arylboronic acid anion. Then, it bonds to the cotton cellulose through a borate ester bond (-BOC-) with the hydroxyl group on the cotton cellulose chain, forming phosphorescent cotton.

[0019] The phosphorescence emission mechanism in this invention is as follows: the conjugated structure in arylboronic acid absorbs ultraviolet light, and π electrons are excited to transition to the excited state (π→π*, S0→Sn, n≥1). The excited state electrons undergo an intersystem crossing process (ISC) from the singlet state to the triplet state (S1→Tn, n≥1). Due to the rigid environment provided by the boron-oxygen bond and the intra- and inter-chain hydrogen bonds of the cotton fiber chain, the electrons finally transition to the ground state (T1→S0) through nonradiative transition. This process is a phosphorescent transition.

[0020] The advantages of this invention are that it uses non-toxic, inexpensive, and readily available organic solvents and substrates, effectively reducing dependence on toxic and expensive organic solvents and inorganic phosphorescent materials. The process of phosphor molecules bonding with hydroxyl groups on the cellulose chains of cotton fabric is simple and rapid. The properties of the treated cotton fabric remain basically unchanged, thus obtaining long-afterglow multicolor phosphorescent cotton fabric. This provides a feasible basis for the large-scale batch processing and application of long-afterglow multicolor phosphorescent textiles.

[0021] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0022] 1. This invention bonds arylboronic acids to the cellulose chains of pure cotton fabrics, utilizing the fine microstructure environment of the fiber to solve the problems of poor solubility, low dyeing rate, low phosphorescence lifetime, and weak and short afterglow of arylboronic acids.

[0023] 2. The reaction conditions of this invention are mild, and the multicolor phosphorescence can be controlled by changing the conjugation degree of the arylboronic acid derivative.

[0024] 3. The present invention adopts a dyeing process, which is simple and easy to prepare on a large scale. Attached Figure Description

[0025] Figure 1 The phosphorescence emission wavelength of cotton fiber (CF);

[0026] Figure 2 The phosphorescence emission wavelength of CF-1Py-B phosphorescent cloth;

[0027] Figure 3 The phosphorescence emission wavelength of CF-Phe9-B phosphorescent cloth;

[0028] Figure 4 The phosphorescence emission wavelength of CF-TP-B phosphorescent cloth;

[0029] Figure 5 The afterglow of three different types of phosphorescent fabric;

[0030] Figure 6 A whiteness data table for three different types of phosphorescent fabrics;

[0031] Figure 7 Photos showing the whiteness of each sample;

[0032] Figure 8 The phosphorescence emission wavelength of CF-multicolor mixed phosphorescent cloth;

[0033] Figure 9 The afterglow of three different types of boric acid mixed phosphorescent cloth;

[0034] Figure 10 Afterglow of Modal phosphorescent cloth prepared from three different types of boric acid;

[0035] Figure 11 Afterglow of silk phosphorescent fabrics prepared from three different types of boric acid. Detailed Implementation

[0036] To make the present invention more apparent and understandable, preferred embodiments are described in detail below with reference to the accompanying drawings.

[0037] Experimental reagents: arylboronic acids (2-triphenylenylboronic acid (TP-B), phenanthrene-9-boronic acid (Phe9-B), 1-pyreneboronic acid (1Py-B)) were all from Shanghai Maclean Biochemical Technology Co., Ltd.; potassium carbonate (K2CO3, Shanghai E. En Chemical Technology Co., Ltd., Ron Reagent); anhydrous ethanol (EtOH, Saen Chemical Technology (Shanghai) Co., Ltd.); deionized water was prepared in-house.

[0038] Example 1: Preparation of Monochromatic Phosphorescent Fabric

[0039] (1) Prepare three working solutions for dyeing solutions respectively. The composition of the working solutions is shown in Table 1.

[0040] Table 1

[0041]

[0042] (2) Weigh arylboronic acid 1Py-B, Phe9-B and TP-B and dissolve them in 1mL of ethanol. Then add 2mL of potassium carbonate aqueous solution (100g / L) to each, stir and sonicate for 1h, heat to dissolve, and keep the temperature at 50℃. Then add a certain amount of deionized water to each until the total volume is 10mL.

[0043] (3) When the working solution temperature rises to 85°C, put the cotton cloth that has been de-scalded and bleached into the working solution, keep it warm for 20 minutes, and then cool it to room temperature.

[0044] (4) Take it out, rinse it with deionized water, dry it (100℃, 60min), and seal it to dry.

[0045] (5) Measure its fluorescence, phosphorescence emission wavelength and whiteness.

[0046] The phosphorescence emission wavelengths of cotton fiber (CF), CF-1Py-B phosphorescent fabric, CF-Phe9-B phosphorescent fabric, and CF-TP-B phosphorescent fabric are as follows: Figure 1-4 As shown. The afterglow of three different types of phosphorescent fabrics as... Figure 5 As shown. The whiteness of CF-TP phosphorescent cloth, CF-Phe9 phosphorescent cloth, and CF-1Py phosphorescent cloth is as follows. Figure 6 As shown. Whiteness photographs of each sample are as follows. Figure 7 As shown.

[0047] Depend on Figure 1-7 The following conclusions can be drawn:

[0048] a. Cotton fibers exhibit phosphorescence emission, with a wavelength of 489 nm, displaying a bluish phosphorescence.

[0049] b. CF-1Py-B phosphorescent cloth has a fluorescence emission wavelength of 512nm and a phosphorescence emission wavelength of 613nm; under 365nm UV lamp irradiation, it exhibits red phosphorescence, corresponding to the phosphorescence emission wavelength; the afterglow can reach 1.6S.

[0050] c.CF-Phe9-B phosphorescent cloth has a fluorescence emission wavelength of 374nm and a phosphorescence emission wavelength of 512nm; under 365nm UV lamp irradiation, it exhibits green phosphorescence, corresponding to the phosphorescence emission wavelength; the afterglow can reach more than 11.4S.

[0051] d.CF-TP-B phosphorescent cloth has a fluorescence emission wavelength of 396nm and a phosphorescence emission wavelength of 487nm; under 365nm UV lamp irradiation, it exhibits red phosphorescence, corresponding to the phosphorescence emission wavelength; the afterglow can reach more than 11.4S, which is longer than that of CF-1Py-B phosphorescent cloth and CF-Phe9-B phosphorescent cloth.

[0052] e. Three different types of phosphorescence were exposed to the atmosphere for 15 days. Among them, the phosphorescence whiteness of CF-1Py-B decreased with increasing intensity; the phosphorescence whiteness of CF-Phe9-B decreased with decreasing intensity, but at a slower rate than that of CF-1Py; the phosphorescence whiteness of CF-TP-B remained basically unchanged and still had a relatively high whiteness.

[0053] Example 2: Preparation of multicolor phosphorescent fabric

[0054] (1) Prepare a mixed working solution of three arylboronic acids for dyeing. The composition of the corresponding arylboronic acid content is shown in Table 2.

[0055] Table 2

[0056]

[0057] (2) Weigh arylboronic acid 1Py-B, Phe9-B and TP-B and dissolve them in 1mL of ethanol. Then add 2mL of potassium carbonate aqueous solution (100g / L), stir and sonicate for 1h, and keep the temperature at 50℃. Then add a certain amount of deionized water to make the total volume 10mL.

[0058] (3) All cotton cloths were thoroughly washed with anhydrous ethanol and air-dried naturally. When the working solution temperature reached 85°C, the cotton cloths were put into the working solution and kept warm for 20 minutes before cooling to room temperature.

[0059] (4) Take it out, rinse it with deionized water, dry it (100℃, 60min), and seal it to dry.

[0060] (5) Determine its fluorescence and phosphorescence emission wavelengths.

[0061] The phosphorescence emission wavelength of CF-multicolor mixed phosphorescent cloth is as follows: Figure 8 As shown. The afterglow of three different types of boric acid mixed phosphorescent cloths as... Figure 9 As shown.

[0062] Depend on Figure 8-9 The following conclusions can be drawn:

[0063] a. When three different types of boric acid are simultaneously applied to cotton fibers, the cotton fabric exhibits multicolor phosphorescence emission.

[0064] b. Its fluorescence emission wavelength is 527nm, and its phosphorescence emission wavelengths are in two bands: 472nm and 617nm, which are consistent with the afterglow of multicolor phosphorescent cotton.

[0065] Example 3: Preparation of Modal phosphorescent fibers

[0066] (1) Prepare a mixed working solution of the three arylboronic acids for the dyeing solution. The composition of the corresponding arylboronic acid content is shown in Table 3.

[0067] Table 3

[0068]

[0069] (1) Weigh arylboronic acid 1Py-B, Phe9-B and TP-B and dissolve them in 1mL of ethanol. Then add 2mL of potassium carbonate aqueous solution (100g / L), stir and sonicate for 1h, and keep the temperature at 50℃. Then add a certain amount of deionized water to make the total volume 10mL.

[0070] (2) All Modal cloths were thoroughly washed with anhydrous ethanol and air-dried naturally. When the working solution temperature reached 85°C, the Modal cloths were put into the working solution and kept warm for 30 minutes before cooling to room temperature.

[0071] (3) Take it out, rinse it with deionized water, dry it (100℃, 60min), seal it and dry it, and take pictures of the afterglow.

[0072] The afterglow of Modal phosphorescent cloth prepared with three different types of boric acid is as follows Figure 10 As shown.

[0073] Depend on Figure 10 The following conclusions can be drawn:

[0074] a. After three different types of boric acid were applied to Modal fabric, the Modal fabric exhibited phosphorescence emission.

[0075] bM-1Py-B phosphorescent fabric exhibits red phosphorescence under 365nm UV light, with an afterglow lasting up to 1.8 seconds.

[0076] cM-Phe9-B phosphorescent fabric exhibits green phosphorescence under 365nm UV light, with an afterglow of up to 16.0S.

[0077] When irradiated with a 365nm UV lamp, the dM-TP-B phosphorescent cloth exhibits red phosphorescence with an afterglow of over 19.0 seconds.

[0078] Example 4: Preparation of Phosphorescent Silk Fibers

[0079] (1) Prepare a mixed working solution of the three arylboronic acids for the dyeing solution. The composition of the corresponding arylboronic acid content is shown in Table 4.

[0080] Table 4

[0081]

[0082]

[0083] (1) Weigh arylboronic acid 1Py-B, Phe9-B and TP-B and dissolve them in 1mL of ethanol. Then add 2mL of potassium carbonate aqueous solution (100g / L), stir and sonicate for 1h, and keep the temperature at 50℃. Then add a certain amount of deionized water to make the total volume 10mL.

[0084] (2) All silk fibers were thoroughly washed with anhydrous ethanol and air-dried naturally. When the temperature of the working solution rose to 85°C, the silk fibers were put into the working solution, kept warm for 30 minutes, and then cooled to room temperature.

[0085] (3) Take it out, rinse it with deionized water, dry it (100℃, 60min), seal it and dry it, and take pictures of the afterglow.

[0086] The afterglow of silk phosphorescent fabrics prepared with three different types of boric acid is like Figure 11 As shown.

[0087] Depend on Figure 11 The following conclusions can be drawn:

[0088] a. When three different types of boric acid are applied to silk fabric, the silk fabric exhibits phosphorescence emission.

[0089] bS-1Py-B phosphorescent cloth exhibits red phosphorescence under 365nm UV light, with an afterglow lasting up to 1.6 seconds.

[0090] cS-Phe9-B phosphorescent fabric exhibits green phosphorescence under 365nm UV light, with an afterglow of over 8.0 seconds.

[0091] When irradiated with a 365nm UV lamp, the dS-TP-B phosphorescent cloth exhibits red phosphorescence with an afterglow of more than 6.0 seconds.

Claims

1. A method for preparing long-afterglow multicolor phosphorescent textiles using arylboronic acid derivatives, characterized in that, Includes the following steps: Step 1): Arylboronic acid, alkali, organic solvent, and water are mixed to prepare different types of arylboronic acid working solutions, which are then ultrasonically vibrated. The arylboronic acid is at least one of 2-triphenylenylboronic acid and phenanthrene-9-boronic acid. When the arylboronic acid is 2-triphenylenylboronic acid, its owf is 0.5-5%; when the arylboronic acid is phenanthrene-9-boronic acid, its owf is 0.5-4%. Step 2): Place the fabric in the arylboric acid working solution, complete the dyeing and fixing in the dyeing machine, and then cool naturally; the fabric includes at least one of cotton, viscose fiber, wool, and silk; the fabric is a pre-treated fabric that has been degreasing and impurity removal; the dyeing and fixing temperature is 80-85℃, and the time is 20-60min; Step 3): Remove the fabric, wash it, and then place it in an oven to dry, obtaining the finished phosphorescent fabric. Seal and dry it.

2. The method for preparing long-afterglow multicolor phosphorescent textiles using arylboronic acid derivatives as described in claim 1, characterized in that, In step 1), the alkali agent is at least one of ammonia, sodium carbonate, sodium bicarbonate, potassium carbonate, and cesium carbonate, and the dosage is 5-40 g / L.

3. The method for preparing long-afterglow multicolor phosphorescent textiles using arylboronic acid derivatives as described in claim 1, characterized in that, In step 1), the organic solvent is at least one of ethanol, methanol, acetone, and tetrahydrofuran.

4. The method for preparing long-afterglow multicolor phosphorescent textiles using arylboronic acid derivatives as described in claim 1, characterized in that, In step 1), the volume ratio of organic solvent to water is 1:9-1:4, and the total amount of organic solvent and water used is 5-20 times the weight of the fabric in step 2).

5. The method for preparing long-afterglow multicolor phosphorescent textiles using arylboronic acid derivatives as described in claim 1, characterized in that, In step 1), the ultrasonic oscillation time is 30-60 minutes.

6. The method for preparing long-afterglow multicolor phosphorescent textiles using arylboronic acid derivatives as described in claim 1, characterized in that, In step 3), the washing method is to rinse with deionized water 4-5 times.

7. The method for preparing long-afterglow multicolor phosphorescent textiles using arylboronic acid derivatives as described in claim 1, characterized in that, In step 3), the drying temperature is 70-105℃ and the time is 30-60min.

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