A fluorescent dye monomer containing a benzopyran structure and a preparation method and application thereof

Abstract

The application provides a fluorescent dye monomer containing a benzopyran structure and a preparation method and application thereof, and has a chemical structure as shown in the formula: wherein R1 and R2 are independently C n H 2n+1 , n is an integer of 1-7; A is O, S or N, and B is O or NH. By introducing a sulfonamide substituent into the fluorescent dye molecule with the benzopyran structure, the solubility of the fluorescent dye molecule in a polymer resin is enhanced, so that the fluorescent dye monomer can be uniformly dispersed in a high-molecular polymer matrix in a molecular form.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of chemical synthesis, and relates to a fluorescent dye monomer, in particular to a fluorescent dye monomer containing a benzopyran structure and a preparation method and application thereof. BACKGROUND

[0002] The fluorescent dye is a very important functional dye, and is widely applied in the industrial, agricultural, medical, textile, energy and national defense departments. Due to the light emitting characteristics of the fluorescent dye, the fluorescent dye has been applied in many fields, and is used as a fluorescent whitening agent, a dyeing dye, a laser dye, and is also applied in fluorescent analysis, fluorescent anti-counterfeiting, tracking detection and energy utilization.

[0003] The fluorescent dye has high color strength and bright color, and is loved by consumers all over the world; and the coumarin fluorescent dye is one of the most important varieties in the fluorescent dye series, has excellent properties such as strong fluorescence and high color strength, and has been highly valued by dye industrial developed countries such as Japan, Germany and Switzerland. Since the 1970s, the coumarin fluorescent dye has developed rapidly, and has been widely applied in the dyeing of polyester fibers and ultra-fine fibers, and can also be used as a fluorescent solvent dye, a fluorescent pigment, a laser dye and a fluorescent tracer targeted therapy, has a wide color spectrum coverage, and has high industrial application value. The coumarin fluorescent dye has the important advantage of good level dyeing when dyeing ultra-fine fibers, but has the disadvantage of poor light resistance, weather resistance and sublimation fastness, which affects its application prospect. SUMMARY

[0004] In order to solve the above technical problems, the present application aims to provide a fluorescent dye monomer containing a benzopyran structure.

[0005] In order to achieve the above technical problems, the present application provides a fluorescent dye monomer containing a benzopyran structure, and the chemical structure formula of the fluorescent dye monomer is as follows:

[0006]

[0007] In the formula, R1 and R2 are independently C n H 2n+1 , n is an integer of 1-7; A is O, S or N, and B is O or NH.

[0008] Another object of the present application is to provide a preparation method of the fluorescent dye monomer containing a benzopyran structure.

[0009] (a) adding chlorosulfonic acid, an auxiliary A and a 9-substituted coumarin dye into a reaction container in sequence to obtain a first mixture; the chemical structure formula of the 9-substituted coumarin dye is as follows:

[0010] (b) heating the first mixture to 80-150°C to react for 1-5 hours, and determining the reaction end point by HPLC detection;

[0011] (c) cooling the product of step (b) to 0-20°C, and then diluting into ice or ice water, filtering to obtain the filter cake, and washing the filter cake with ice water until neutral;

[0012] (d) putting the filter cake into a reactor, adding N-methyl pyrrolidone to stir and pulp, adding acrylamide and propane sulfonol at room temperature respectively, reacting for 1-2 hours at room temperature respectively, adding water to precipitate yellow crystalline material, and filtering and washing to obtain the fluorescent dye monomer.

[0013] Optimally, in step (a), the mass ratio of the chlorosulfonic acid, the auxiliary A and the 9-substituted coumarin dye is 1-3:0.1-1:1.

[0014] Further, in step (a), the mass ratio of the chlorosulfonic acid, the auxiliary A and the 9-substituted coumarin dye is 2.5:0.3:1.

[0015] Optimally, the auxiliary A is a mixture of sulfurous acid chloride, sulfurous oxide or sulfur dioxide and chlorine gas, preferably sulfurous acid chloride.

[0016] Optimally, in step (b), the heating is to 100-130°C for reaction.

[0017] Optimally, in step (d), the mass ratio of the N-methyl pyrrolidone, acrylamide and propane sulfonol is 1-3:1-3:2-5.

[0018] Further, in step (d), the mass ratio of the N-methyl pyrrolidone, acrylamide and propane sulfonol is 1.5:1:2.

[0019] Still another object of the present application is to provide an application of the fluorescent dye monomer containing the benzopyran structure as described above, comprising the following steps: dispersing the fluorescent dye monomer containing the benzopyran structure in water, adding acrylonitrile or acrylic acid dropwise, adding a persulfate initiator under stirring, and allowing a polymerization reaction to occur at room temperature to form polymer dye particles, and cooling, filtering and washing.

[0020] Optimally, the weight ratio of the fluorescent dye monomer containing the benzopyran structure and water is 1:50-100, and the weight ratio of the fluorescent dye monomer containing the benzopyran structure, acrylonitrile or acrylic acid and persulfate is 1:1-4:0.02-0.05.

[0021] This invention relates to a fluorescent dye monomer containing a benzopyran structure. By introducing sulfonamide substituents into the benzopyran fluorescent dye molecule, the solubility of the fluorescent dye molecule in polymer resin is enhanced, allowing the fluorescent dye monomer to be uniformly dispersed in the polymer matrix in molecular form. The maximum absorption wavelength of the dye molecule undergoes a significant red shift, the molar absorptivity of the dye increases, and the dyeing rate on polyester is significantly improved, reaching over 95% without the addition of special dyeing auxiliaries. Simultaneously, the application performance of the dye is improved, significantly enhancing the lightfastness and sublimation fastness of the fluorescent dye. Furthermore, the introduction of sulfonamide substituents into the benzopyran fluorescent dye molecule... The tertiary amine structure with saturated double bonds gives the molecular structure amphiphilicity, greatly expanding its polymerization range. Different types of hydrophilic or lipophilic fluorescent polymers can be obtained by changing the type of monomer. The preparation method of the fluorescent dye monomer containing the benzopyran structure of this invention is simple and has a high yield. In addition, the polymerization reaction conditions are mild and controllable during application. The monomer can be added gradually, which makes it easy to control the reaction temperature. No other organic solvents or emulsifiers are needed during the entire polymerization process. The obtained fluorescent polymer product is pure and has significantly improved application performance such as solvent resistance, light and weather resistance, migration resistance, and sublimation fastness compared with monomer dyes. Attached Figure Description

[0022] Figure 1 This diagram illustrates the preparation process and application of the fluorescent dye monomers and polymers containing the benzopyran structure of this invention.

[0023] Figure 2 The NMR spectrum of the fluorescent dye monomer containing the benzopyran structure of this invention is shown below. 1 H NMR);

[0024] Figure 3 The HPLC spectrum of the fluorescent dye monomer containing the benzopyran structure of this invention is shown.

[0025] Figure 4 The NMR spectrum of the fluorescent dye polymer containing the benzopyran structure of this invention is shown below. 1 H NMR);

[0026] Figure 5 This is the mass spectrum of the fluorescent dye polymer containing a benzopyran structure of the present invention. Detailed Implementation

[0027] The fluorescent dye monomer containing a benzopyran structure of the present invention has the following general chemical formula:

[0028]

[0029] In the formula, R1 and R2 are independent of each other and are C n H2n+1 By introducing sulfonamide substituent into the fluorescent dye molecule with benzopyran structure, the solubility of the fluorescent dye molecule in polymer resin is enhanced, so that the fluorescent dye monomer can be uniformly dispersed in the polymer matrix in molecular form; the maximum absorption wavelength of the dye molecule is obviously red-shifted, the molar absorption coefficient of the dye is increased, the dyeing rate on polyester is greatly improved, and the dyeing rate can reach more than 95% without adding special printing and dyeing auxiliaries; meanwhile, the application performance of the dye is improved, so that the lightfastness and sublimation fastness of the fluorescent dye are obviously improved; meanwhile, after introducing tertiary amine structure with unsaturated double bond into the fluorescent dye molecule with benzopyran structure, the molecule structure has water-oil amphiphilicity, the polymerization range of the molecule is greatly expanded, and different types of hydrophilic or lipophilic fluorescent polymers can be obtained by changing the type of monomer.

[0030] The preparation method of the fluorescent dye monomer with benzopyran structure comprises the following steps: (a) adding chlorosulfonic acid, an auxiliary A and 9-substituted coumarin dye into a reaction container in sequence to obtain a first mixture; the chemical structural formula of the 9-substituted coumarin dye is (b) heating the first mixture to 80-150 ℃ for 1-5 hours to determine the reaction end point by HPLC detection; (c) cooling the product of step (b) to 0-20 ℃, then diluting into ice or ice water, filtering to obtain a filter cake, and washing the filter cake with ice water until neutral; (d) putting the filter cake into a reactor, adding N-methyl pyrrolidone to stir and pulp, adding acrylamide and propane sulfonol at room temperature respectively, reacting for 1-2 hours at room temperature respectively, adding water to precipitate yellow crystalline material, and filtering and washing to obtain the fluorescent dye monomer. The method has simple process and high yield. In step (a), the mass ratio of the chlorosulfonic acid, the auxiliary A and the 9-substituted coumarin dye is 1-3:0.1-1:1, and is preferably 2.5:0.3:1. The auxiliary A is chlorosulfonic acid, sulfurous acid or a mixture of sulfur dioxide and chlorine gas, and is preferably chlorosulfonic acid. In step (b), the heating is performed to 100-130 ℃, and the reaction is maintained for 1-3 hours; preferably, the heating is performed to 120 ℃, and the reaction is maintained for 2 hours. In step (c), the cooling is preferably to 10 ℃. In step (d), the mass ratio of the N-methyl pyrrolidone, the acrylamide and the propane sulfonol is 1-3:1-3:2-5, and is preferably 1.5:1:2.

[0031] The application of the above-mentioned fluorescent dye monomer with benzopyran structure includes the following steps: dispersing the fluorescent dye monomer with benzopyran structure in water, dropwise adding acrylonitrile or acrylic acid, adding persulfate initiator under stirring, and performing polymerization reaction at room temperature to form polymer dye particles, and then cooling, filtering and washing. Preferably, the weight ratio of the fluorescent dye monomer with benzopyran structure to water is 1:50-100, preferably 1:80; the weight ratio of the fluorescent dye monomer with benzopyran structure to acrylonitrile or acrylic acid, persulfate is 1:1-4:0.02-0.05, preferably 1:2:0.03.

[0032] The application will be further described in conjunction with the embodiments shown in the accompanying drawings.

[0033] Example 1

[0034] The present embodiment provides a fluorescent dye monomer with benzopyran structure, a preparation method and an application thereof, as shown in Figure 1 The application includes the following steps:

[0035] (a) adding chlorosulfonic acid 25 g, sulfurous chloride 3 g and 9-substituted coumarin dye 10 g (as shown in CAS: 52372-39-1; that is, R1, R2 are ethyl, A is N, and B is imino group) into a reaction container in sequence to obtain a first mixture;

[0036] (b) heating the first mixture to 120°C to perform reaction and maintaining for 2 hours, and determining the reaction end point by HPLC detection; the specific principle is as follows:

[0037]

[0038] (c) cooling the product of step (b) to 10°C, diluting the mixture into 200 g of crushed ice, filtering to obtain a filter cake, and washing the filter cake with ice water until neutral;

[0039] (d) putting the filter cake into a reactor, adding NMP (N-methyl pyrrolidone) 15 g to stir and pulp; adding acrylamide 10 g at room temperature to stir and react for 2 hours; further adding propanesulfonic acid lactone 20 g and sodium hydroxide to stir and react for 2 hours under alkaline condition (pH is 8), adding water 20 g to precipitate yellow crystalline material, and filtering and washing to obtain the fluorescent dye monomer (13.5 g, yield is about 81%, HPLC purity is 97.6%; that is, the fluorescent dye monomer with benzopyran structure, as shown in Figure 2 and Figure 3 ); the specific principle is as follows:

[0040]

[0041] (e) 8 g of the fluorescent dye monomer is dispersed in 800 g of water, 20 g of acrylonitrile is added dropwise, 0.3 g of sodium persulfate powder is added under sufficient stirring, and polymerization occurs at room temperature. The temperature of the system rises slightly, and the polymer dye particles are gradually formed within 1-2 hours. After cooling, filtration and washing, the oleophilic polymer polymeric dye is obtained (see the test in Figure 4 and Figure 5 ).

[0042] Example 2

[0043] This example provides a fluorescent dye monomer containing a benzopyran structure, a preparation method and applications thereof, which are basically the same as those in Example 1, except that in step (a), 10 g of chlorosulfonic acid, 10 g of sulfurous acid chloride and 10 g of 9-substituted coumarin dye are sequentially added to the reaction vessel.

[0044] After filtration and washing, 10.61 g of the fluorescent dye monomer is obtained, with a yield of about 64% and an HPLC purity of 94.0%.

[0045] Example 3

[0046] This example provides a fluorescent dye monomer containing a benzopyran structure, a preparation method and applications thereof, which are basically the same as those in Example 1, except that in step (a), 30 g of chlorosulfonic acid, 1 g of sulfurous acid chloride and 10 g of 9-substituted coumarin dye are sequentially added to the reaction vessel.

[0047] After filtration and washing, 13.26 g of the fluorescent dye monomer is obtained, with a yield of about 80% and an HPLC purity of 95.9%.

[0048] Example 4

[0049] This example provides a fluorescent dye monomer containing a benzopyran structure, a preparation method and applications thereof, which are basically the same as those in Example 1, except that in step (a), 3 g of sulfurous acid anhydride is added to the reaction vessel.

[0050] After filtration and washing, 13.19 g of the fluorescent dye monomer is obtained, with a yield of about 79% and a purity of 96.1%.

[0051] Example 5

[0052] This example provides a fluorescent dye monomer containing a benzopyran structure, a preparation method and applications thereof, which are basically the same as those in Example 1, except that in step (a), a mixture of sulfur dioxide and chlorine gas 3 g (mass ratio 1:1) is added to the reaction vessel.

[0053] After filtration and washing, 13.94 g of the fluorescent dye monomer is obtained, with a yield of about 84% and a purity of 93.2%.

[0054] Example 6

[0055] The embodiment provides a fluorescent dye monomer containing a benzopyran structure, a preparation method and application thereof, which are basically identical with those in the embodiment 1, except that in step (b), the first mixture is heated to 80 DEG C to react and maintained for 5 hours.

[0056] The fluorescent dye monomer is obtained by filtration and washing, with a yield of about 77%, and a purity of 96.2%.

[0057] Embodiment 7

[0058] The embodiment provides a fluorescent dye monomer containing a benzopyran structure, a preparation method and application thereof, which are basically identical with those in the embodiment 1, except that in step (b), the first mixture is heated to 150 DEG C to react and maintained for 1 hour.

[0059] The fluorescent dye monomer is obtained by filtration and washing, with a yield of about 79%, and a purity of 93.3%.

[0060] Embodiment 8

[0061] The embodiment provides a fluorescent dye monomer containing a benzopyran structure, a preparation method and application thereof, which are basically identical with those in the embodiment 1, except that in step (d), NMP (N-methyl pyrrolidone) 30 g is added to stir and beat, acrylamide 10 g and propane sulfonol 50 g are added at room temperature,

[0062] The fluorescent dye monomer is obtained by filtration and washing, with a yield of about 75%, and a purity of 96.9%.

[0063] Embodiment 9

[0064] The embodiment provides a fluorescent dye monomer containing a benzopyran structure, a preparation method and application thereof, which are basically identical with those in the embodiment 1, except that in step (d), NMP (N-methyl pyrrolidone) 5.3 g is added to stir and beat, acrylamide 10 g and propane sulfonol 35 g are added at room temperature,

[0065] The fluorescent dye monomer is obtained by filtration and washing, with a yield of about 66%, and a purity of 91.4%.

[0066] Embodiment 10

[0067] The embodiment provides application of a fluorescent dye monomer containing a benzopyran structure, which is basically identical with that in the embodiment 1, except that in step (e), 8 g of the fluorescent dye monomer is dispersed in 800 g of water, and 8 g of acrylonitrile is added dropwise.

[0068] Embodiment 11

[0069] The present example provides an application of a fluorescent dye monomer containing a benzopyran structure, which is basically the same as that in Example 1, except that in step (e), 8 g of the fluorescent dye monomer is dispersed in 800 g of water, and 32 g of acrylonitrile is added dropwise.

[0070] Comparative Example 1

[0071] The present example provides a fluorescent dye monomer containing a benzopyran structure, a preparation method thereof, and an application thereof, which are basically the same as those in Example 1, except that in step (d), no propane sulfonol is added.

[0072] The polymer dyes prepared in Examples 1-12 and Comparative Example 1 are subjected to application tests, and the results are shown in Table 1.

[0073] Table 1 Application performance of the polymer dyes prepared in Examples 1-12 and Comparative Example 1

[0074]

[0075]

[0076] The test method for the dye-uptake rate is in accordance with GB / T9337-2009.

[0077] The test method for the maximum absorption wavelength is as follows: 0.020 g of the dye (high-molecular polymer dye) is accurately weighed in a beaker, dissolved by mixing with a small amount of distilled water, and then transferred to a 250 ml capacity bottle, which is diluted to the mark with distilled water, and mixed well for use. 25.00 ml, 20.00 ml, 15.00 ml, 10.00 ml, 5.00 ml, and 2.50 ml of the above solution are respectively taken with a pipette into 50 ml capacity bottles numbered 1-6, and diluted to the mark with distilled water. One of the dye solutions with a certain concentration is selected, and the absorbance of the dye is scanned at different wavelengths of 380-780 nm every 10 nm by using a trial method on an ultraviolet-visible spectrophotometer. Finally, the maximum absorption wavelength of the dye is found at the maximum absorbance.

[0078] The test method for the molar absorption coefficient Lmol-1cm-1is as follows: 0.020 g of the dye is accurately weighed in a beaker, dissolved by mixing with a small amount of distilled water, and then transferred to a 250 ml capacity bottle, which is diluted to the mark with cyclohexane, and mixed well for use. Part of the sample is placed in a 1 cm quartz absorption cell, and cyclohexane is used as a blank reference. The quartz cell is placed in an ultraviolet spectrophotometer to measure the absorbance A of the solution. According to the Beer's law, ε = A / lc (wherein l is the thickness of the quartz cell; c is the molar concentration of the solution)

[0079] The test method for light resistance (grade) is as follows: the xenon lamp flash method is used for testing, and the color change is evaluated by using a blue wool scale, with 8 being the best and 1 being the worst, in accordance with the ISO105B02 standard.

[0080] Test for fastness to sublimation according to GB 5718-1997

[0081] Test for fastness to solvents according to GB 5211.9-85

[0082] Test for fastness to migration according to German Industrial Standard DIN 53.775: The colored sheet to be tested is placed together with a soft PVC sheet containing 5% titanium dioxide at a pressure of 1 kg / cm 2 , a temperature of 80°C and a time of 24 hours. The degree of contamination of the white sheet is evaluated on a scale of 1 to 5, with 5 indicating no migration.

[0083] The above examples are only for illustrating the technical concept and characteristics of the present application, and the purpose is to enable those skilled in the art to understand the content of the present application and to implement it, and cannot limit the protection scope of the present application. Any equivalent changes or modifications made according to the spirit and essence of the present application shall be covered within the protection scope of the present application.

Claims

1. A fluorescent dye monomer containing a benzopyran structure, characterized by Its chemical structure general formula is: wherein R1and R2are independently of each other C n H 2n+1 n is an integer from 1 to 7; A is N and B is O or NH.

2. The method of claim 1, wherein the preparation of the monomer of the fluorescent dye having the structure of benzopyran is characterized by, The method comprises the following steps: (a) adding chlorosulfonic acid, an auxiliary A and a 9-substituted coumarin dye into a reaction vessel in sequence to obtain a first mixture; the chemical structural formula of the 9-substituted coumarin dye is the auxiliary A is thionyl chloride or sulfoxide, or the auxiliary A is a mixture of sulfur dioxide and chlorine; (b) heating the first mixture to 80-150 DEG C to react for 1-5 hours, and determining the reaction end point by HPLC detection; (c) cooling the product of step (b) to 0-20 DEG C, diluting into ice or ice water, filtering to obtain filter cake, and washing the filter cake with ice water until neutral; (d) putting the filter cake into a reactor, stirring and slushing by adding N-methyl pyrrolidone, adding acrylamide and propane sulfonol at room temperature respectively, reacting for 1-2 hours at room temperature respectively, adding water to precipitate yellow crystalline material, and filtering and washing to obtain the fluorescent dye monomer.

3. The method for preparing a fluorescent dye monomer containing a benzopyran structure according to claim 2, characterized in that: In step (a), the mass ratio of the chlorosulfonic acid, the auxiliary A and the 9-substituted coumarin dye is 1-3:0.1-1:

1.

4. The method for preparing a fluorescent dye monomer containing a benzopyran structure according to claim 3, characterized in that: In step (a), the mass ratio of the chlorosulfonic acid, the auxiliary A and the 9-substituted coumarin dye is 2.5:0.3:

1.

5. The method for preparing a fluorescent dye monomer containing a benzopyran structure according to claim 2 or 3, characterized in that: The auxiliary A is thionyl chloride.

6. The method for preparing a fluorescent dye monomer containing a benzopyran structure according to claim 2, characterized in that: In step (b), the heating is to 100-130 DEG C.

7. The method for preparing a fluorescent dye monomer containing a benzopyran structure according to claim 2, characterized in that: In step (d), the mass ratio of the N-methyl pyrrolidone, the acrylamide and the propane sulfonol is 1-3:1-3:2-5.

8. The method for preparing a fluorescent dye monomer containing a benzopyran structure according to claim 7, characterized in that: In step (d), the mass ratio of the N-methyl pyrrolidone, the acrylamide and the propane sulfonol is 1.5:1:

2.

9. Use of the fluorescent monomer having a benzopyran structure according to claim 1, characterized in that, The method comprises the following steps: The fluorescent dye monomer containing the benzopyran structure is dispersed in water, acrylonitrile or acrylic acid is added dropwise, and a persulfate initiator is added under stirring to form polymer dye particles by polymerization reaction at room temperature, and the polymer dye particles are cooled, filtered and washed.

10. Use of the fluorescent monomer containing a benzopyran structure according to claim 9, characterized in that: The weight ratio of the fluorescent dye monomer containing the benzopyran structure to water is 1:50-100, and the weight ratio of the fluorescent dye monomer containing the benzopyran structure to acrylonitrile or acrylic acid and the persulfate is 1:1-4:0.02-0.05.

Images