Method for preparing long-afterglow multicolor phosphorescent textile by using arylboronic acid derivative

Abstract

The invention discloses a method for preparing a long-afterglow multicolor phosphorescent textile by using an arylboronic acid derivative. The method comprises the following steps: preparing arylboronic acid, an alkaline agent, an organic solvent and water into different types of arylboronic acid working solutions, and carrying out ultrasonic oscillation; putting the fabric into the arylboronic acid working solution, finishing dyeing and fixation in a dyeing machine, and then taking out and naturally cooling; and taking out the fabric, washing, drying in a drying oven to obtain a phosphorescent fabric finished product, and sealing and drying. After the treatment, the arylboronic acid and the derivatives thereof can react with fiber macromolecules in a water phase to form covalent bonds, so that the high-fastness long-afterglow phosphorescent emission textile can be obtained. Multicolor phosphorescent textiles can be prepared by adjusting the types of arylboronic acid and derivatives thereof, and can be applied to the fields of anti-counterfeiting, marking and the like. The multicolor phosphorescent textile is prepared from cheap and available raw materials, is low in cost and small in environmental harm, and can be applied to large-scale batch processing.

Description

Technical Field

[0001] The invention belongs to the field of textile printing and dyeing and luminous anti-counterfeiting, and particularly relates to a method for preparing long-afterglow multicolor phosphorescent textiles by using aromatic boronic acid derivatives. Background Art

[0002] The long life of room temperature phosphorescent (RTP) materials has shown a wide range of application prospects in optoelectronics, sensing, bio-imaging, and advanced security and anti-counterfeiting. However, the traditional petroleum-based room temperature phosphorescent materials have defects such as expensive and toxic organic solvents, strict reaction conditions, and difficulty in degrading petroleum-based materials, which limit their practical value. Polysaccharide-based materials are green, environmentally friendly, renewable raw materials, and biodegradable, and are an important direction for the development of the international new materials industry.

[0003] At present, there are many materials for polysaccharide-based room temperature phosphorescence, such as cellulose, lignin, starch and sodium alginate, which have many related reports. However, the disadvantages of these materials, such as microcrystallization, harsh reaction conditions and short luminescence lifetime, greatly increase the difficulty of preparation, which is not conducive to the requirements of green environmental protection and sustainable development. Therefore, it is of great practical significance to develop an environmentally friendly, degradable and adjustable multi-color phosphorescent textile. Arylboronic acid and its derivatives as phosphor molecules contain benzene rings with different degrees of conjugation, so that the prepared phosphorescent fabric has long afterglow multi-color adjustable RTP emission characteristics, and also has the characteristics of stability, low toxicity and environmental friendliness, which makes it of great value in the research and application of organic small molecule room temperature phosphorescent materials. Cellulose fibers have intrachain hydrogen bonds, interchain hydrogen bonds, hydrogen bonds in crystalline and non-crystalline regions, and non-centrosymmetrically arranged hydrogen bonds, which give the cellulose chains 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 the phosphorescence lifetime and achieving long-lasting 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-lasting multicolor phosphorescent textiles by using aromatic boronic acid derivatives.

[0005] In order to solve the above problems, the present invention provides a method for preparing long-lasting multicolor phosphorescent textiles using aromatic boronic acid derivatives, comprising the following steps:

[0006] Step 1): preparing different types of aryl boronic acid working solutions by mixing aryl boronic acid, alkali, organic solvent and water and subjecting them to ultrasonic vibration;

[0007] Step 2): placing the fabric in the aromatic boric acid working solution, dyeing and fixing the fabric in a dyeing machine, and then taking the fabric out and cooling it naturally;

[0008] Step 3): Take out the fabric, wash it, and then put it in an oven to dry it to obtain a phosphorescent fabric product, which is then sealed and dried.

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

[0010] Preferably, in step 1), the alkaline agent is at least one of ammonia water, sodium carbonate, sodium bicarbonate, potassium carbonate and cesium carbonate, and the amount used 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 the organic solvent to water is 1:9-1:4, and the total amount of the organic solvent and water is 5-20 times the weight of the fabric in step 2).

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

[0014] Preferably, in step 2), the fabric comprises at least one of cotton, viscose fiber, wool, silk and polyamide fiber; and the fabric is fabric that has been pre-treated for degreasing and removing impurities.

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

[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° C. and the drying time is 30-60 min.

[0018] The BO bond bonding mechanism in the present invention is as follows: first, under alkaline conditions (pH ≥ 10), the boron atom of the aromatic boronic acid derivative phosphor molecule provides an empty orbital to coordinate with the lone pair of electrons provided by the oxygen atom on OH- to form an aromatic boronic acid anion, which then bonds to the cotton cellulose through a borate ester bond (-BOC-) with the hydroxyl group on the cotton cellulose chain to form phosphorescent cotton.

[0019] The phosphorescence emission mechanism of the present invention is as follows: the conjugated structure in the aromatic boronic acid absorbs ultraviolet light, the π electron is excited and transitions to an excited state (π→π*, S0→Sn, n≥1), the excited state electron singlet intersystem crossing process (ISC) to a triplet state (S1→Tn, n≥1), the boron oxygen bond and the hydrogen bonds within and between the cotton fiber chains provide a rigid environment, and finally the electron transitions to the ground state (T1→S0) through a non-radiative transition, and the process is transitioned in the form of phosphorescence.

[0020] The advantages of the present invention are that non-toxic, cheap and easily available organic solvents and substrates are used, which effectively reduces the dependence on toxic and expensive organic solvents and inorganic phosphorescent materials. The bonding process between phosphor molecules and hydroxyl groups on cellulose chains of cotton fabrics is simple and the reaction is rapid. The properties of the treated cotton fabric itself remain basically unchanged, and long-lasting multi-color phosphorescent cotton fabric can be obtained, which provides a feasible basis for large-scale batch processing and application of long-lasting multi-color phosphorescent textiles.

[0021] Compared with the prior art, the present invention has the following beneficial effects:

[0022] 1. The present invention bonds aromatic boronic acids to the cellulose chains of pure cotton fabrics and utilizes the fine microstructure environment of the fibers to solve the problems of poor solubility, low dye uptake, low phosphorescence lifetime, and weak and short afterglow of aromatic boronic acids.

[0023] 2. The reaction conditions of the present invention are mild, and the regulation of multicolor phosphorescence can be achieved by changing the conjugation degree of the aromatic boronic acid derivatives.

[0024] 3. The present invention adopts a dyeing processing route, which is simple and easy to prepare on a large scale. BRIEF DESCRIPTION OF THE DRAWINGS

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

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

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

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

[0029] Figure 5 The afterglow of 3 different types of phosphorescent cloth;

[0030] Figure 6 This is a whiteness data table for 3 different types of phosphorescent fabrics;

[0031] Figure 7 is the whiteness photo of each sample;

[0032] Figure 8 is the phosphorescence emission wavelength of the CF-multicolor hybrid phosphorescent cloth;

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

[0034] Fig.10 Afterglow of Modal phosphorescent cloth prepared with 3 different types of boric acid;

[0035] Fig.11 Afterglow of silk phosphorescent cloth prepared with three different types of boric acid. DETAILED DESCRIPTION

[0036] In order to make the present invention more clearly understood, preferred embodiments are described in detail below with reference to the accompanying drawings.

[0037] Experimental drugs: aryl boronic acids (2-triphenylboronic acid (TP-B), phenanthrene-9boronic acid (Phe9-B), 1-pyreneboronic acid (1Py-B)) were all from Shanghai MacLean Biochemical Technology Co., Ltd.; potassium carbonate (K2CO3, Ron reagent from Shanghai Eon Chemical Technology Co., Ltd.); anhydrous ethanol (EtOH, San Chemical Technology (Shanghai) Co., Ltd.); deionized water was homemade.

[0038] Example 1: Preparation of Monochrome Phosphorescent Fabric

[0039] (1) Prepare three dye working solutions respectively. The compositions of the corresponding dye working solutions are shown in Table 1.

[0040] Table 1

[0041]

[0042] (2) Weigh 1Py-B, Phe9-B, and TP-B of aromatic boronic acid and dissolve them in 1 mL of ethanol, then add 2 mL of potassium carbonate aqueous solution (100 g / L) respectively, stir and ultrasonicate for 1 h, heat to dissolve, and keep the temperature at 50°C; then add a certain amount of deionized water to make the total volume 10 mL.

[0043] (3) When the working liquid temperature rises to 85°C, put the cotton cloth after descaling and bleaching into the working liquid, keep the temperature for 20 minutes, and cool to room temperature;

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

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

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

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

[0048] a. Cotton fiber has the phenomenon of phosphorescence emission, and its phosphorescence emission wavelength is 489nm, showing cyan phosphorescence

[0049] b. The fluorescence emission wavelength of CF-1Py-B phosphorescent cloth is 512nm, and the phosphorescence emission wavelength is 613nm. Under the irradiation of 365nm UV light, it shows red phosphorescence, which corresponds to the phosphorescence emission wavelength; the afterglow can reach 1.6S.

[0050] c. The fluorescence emission wavelength of CF-Phe9-B phosphorescent cloth is 374nm, and the phosphorescence emission wavelength is 512nm. Under the irradiation of 365nm UV light, it shows green phosphorescence, which corresponds to the phosphorescence emission wavelength. The afterglow can reach more than 11.4S.

[0051] d. The fluorescence emission wavelength of CF-TP-B phosphorescent cloth is 396nm, and the phosphorescence emission wavelength is 487nm. Under the irradiation of 365nm UV light, it shows red phosphorescence, which corresponds to the phosphorescence emission wavelength. The afterglow can reach more than 11.4S, which is longer than the afterglow of CF-1Py-B phosphorescent cloth and CF-Phe9-B phosphorescent cloth.

[0052] e. The three different types of phosphorescence were exposed to the atmosphere for 15 days. The whiteness of the CF-1Py-B phosphorescence cloth became lower and lower. The whiteness of the CF-Phe9-B phosphorescence cloth became lower and lower, and decreased more slowly than that of the CF-1Py phosphorescence cloth. The whiteness of the CF-TP-B phosphorescence cloth remained basically unchanged and still had a relatively high whiteness.

[0053] Example 2: Preparation of multi-color phosphorescent fabric

[0054] (1) Prepare a dye solution by mixing three kinds of aromatic boronic acids together. The corresponding aromatic boronic acid content composition is shown in Table 2.

[0055] Table 2

[0056]

[0057] (2) Weigh 1Py-B, Phe9-B, and TP-B of aromatic boronic acid and dissolve them in 1 mL of ethanol. Then add 2 mL of potassium carbonate aqueous solution (100 g / L). Stir and ultrasonicate for 1 h while maintaining the temperature at 50°C. Then add a certain amount of deionized water to make the total volume 10 mL.

[0058] (3) All cotton cloths were thoroughly washed with anhydrous ethanol and dried naturally; when the working solution temperature rose to 85°C, the cotton cloths were placed in the working solution, kept warm for 20 minutes, and then cooled to room temperature;

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

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

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

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

[0063] a. After three different types of boric acid are dyed onto cotton fibers simultaneously, the cotton fabric exhibits multi-color phosphorescence emission.

[0064] b. Its fluorescence emission wavelength is at 527nm, and its phosphorescence emission wavelength is at 472nm and 617nm, which is consistent with the afterglow of multi-color phosphorescent cotton.

[0065] Example 3: Preparation of Modal Phosphorescent Fiber

[0066] (1) Prepare a dye solution containing three kinds of aromatic boronic acids mixed together. The corresponding aromatic boronic acid content composition is shown in Table 3

[0067] Table 3

[0068]

[0069] (1) Weigh 1Py-B, Phe9-B, and TP-B of aromatic boronic acid and dissolve them in 1 mL of ethanol. Then add 2 mL of potassium carbonate aqueous solution (100 g / L). Stir and ultrasonicate for 1 h while maintaining the temperature at 50°C. Then add a certain amount of deionized water to make the total volume 10 mL.

[0070] (2) All Modal cloths were thoroughly washed with anhydrous ethanol and dried naturally; when the working liquid temperature rose to 85°C, the Modal cloths were placed in the working liquid, kept warm for 30 minutes, and then cooled to room temperature;

[0071] (3) Take out the tube, rinse it with deionized water, dry it (100°C, 60 min), seal it and dry it, and photograph its afterglow.

[0072] The afterglow of Modal phosphorescent cloth prepared with three different types of boric acid is shown in Figure 2. Fig.10 shown.

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

[0074] a. After three different types of boric acid were dyed onto Modal cloth, the Modal cloth had phosphorescent emission.

[0075] When illuminated by 365nm UV light, bM-1Py-B phosphorescent cloth shows red phosphorescence, and the afterglow can reach 1.8S.

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

[0077] Under the irradiation of 365nm UV lamp, dM-TP-B phosphorescent cloth shows red phosphorescence, and the afterglow can reach more than 19.0S.

[0078] Example 4: Preparation of silk phosphorescent fibers

[0079] (1) Prepare a dye solution containing three kinds of aromatic boronic acids mixed together. The corresponding aromatic boronic acid content composition is shown in Table 4

[0080] Table 4

[0081]

[0082]

[0083] (1) Weigh 1Py-B, Phe9-B, and TP-B of aromatic boronic acid and dissolve them in 1 mL of ethanol. Then add 2 mL of potassium carbonate aqueous solution (100 g / L). Stir and ultrasonicate for 1 h while maintaining the temperature at 50°C. Then add a certain amount of deionized water to make the total volume 10 mL.

[0084] (2) All silk fibers were thoroughly washed with anhydrous ethanol and dried naturally; when the working solution temperature rose to 85°C, the silk fibers were placed in the working solution, kept warm for 30 minutes, and then cooled to room temperature;

[0085] (3) Take out the tube, rinse it with deionized water, dry it (100°C, 60 min), seal it and dry it, and photograph its afterglow.

[0086] The afterglow of silk phosphorescent cloth prepared with three different types of boric acid is shown in Figure 2. Fig.11 shown.

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

[0088] a. After three different types of boric acid were dyed onto silk cloth, the silk cloth showed phosphorescence emission.

[0089] When illuminated by 365nm UV light, bS-1Py-B phosphorescent cloth shows red phosphorescence, and the afterglow can reach 1.6S.

[0090] Under 365nm UV light, cS-Phe9-B phosphorescent cloth exhibits green phosphorescence, and the afterglow can reach more than 8.0S.

[0091] Under the irradiation of 365nm UV light, dS-TP-B phosphorescent cloth shows red phosphorescence, and the afterglow can reach more than 6.0S.

Claims

1. A method for preparing long-lasting multicolor phosphorescent textiles using aromatic boronic acid derivatives, characterized in that: The following steps are involved: Step 1): preparing different types of aryl boronic acid working solutions by mixing aryl boronic acid, alkali, organic solvent and water and subjecting them to ultrasonic vibration; Step 2): placing the fabric in the aromatic boric acid working solution, dyeing and fixing the fabric in a dyeing machine, and then taking the fabric out and cooling it naturally; Step 3): Take out the fabric, wash it, and then put it in an oven to dry it to obtain a phosphorescent fabric product, which is then sealed and dried.

2. The method for preparing long-lasting multicolor phosphorescent textiles using arylboronic acid derivatives according to claim 1, characterized in that: In the step 1), the aryl boronic acid is at least one of 2-triphenylboronic acid, phenanthrene-9boric acid, and 1-pyreneboric acid; when the aryl boronic acid is 2-triphenylboric acid, its usage amount owf is 0.5-5%; when the aryl boronic acid is phenanthrene-9boric acid, its usage amount owf is 0.5-4%; when the aryl boronic acid is 1-pyreneboric acid, its usage amount owf is 0.5-3%.

3. The method for preparing long-lasting multicolor phosphorescent textiles using arylboronic acid derivatives according to claim 1, characterized in that: In the step 1), the alkaline agent is at least one of ammonia water, sodium carbonate, sodium bicarbonate, potassium carbonate and cesium carbonate, and the amount used is 5-40 g / L.

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

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

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

7. The method for preparing long-lasting multicolor phosphorescent textiles using arylboronic acid derivatives according to claim 1, characterized in that: In the step 2), the fabric comprises at least one of cotton, viscose fiber, wool, silk and polyamide fiber; and the fabric is fabric that has been pre-treated for degreasing and removing impurities.

8. The method for preparing long-lasting multicolor phosphorescent textiles using arylboronic acid derivatives as claimed in claim 1, characterized in that: In the step 2), the temperature for dyeing and fixing is 80-85°C and the time is 20-60 minutes.

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

10. The method for preparing long-lasting multicolor phosphorescent textiles using arylboronic acid derivatives according to claim 1, characterized in that: In the step 3), the drying temperature is 70-105° C. and the drying time is 30-60 min.

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