阅读说明：本技术 一类含有氨基的萘酰亚胺类染料在超临界co2中的合成与染色方法 (Naphthalimide dyes containing amino in supercritical CO2The synthesis and dyeing method of ) 是由 熊小庆 候俊 郑来久 吕丽华 林春迎 闫俊 赵虹娟 郑环达 付德阳 于 2021-09-10 设计创作，主要内容包括：本发明公开了一类含有氨基的萘酰亚胺类染料在超临界CO-(2)中的合成与染色方法,以超临界二氧化碳(CO-(2))为溶剂,以硝基取代的萘酰亚胺类化合物为染料前驱体,Au/TiO-(2)作为催化剂,H-(2)作为还原剂,不同温度、压力和时间条件下,实现超临界CO-(2)中萘酰亚胺类荧光染料的合成与纺织品染色同步的方法。所述的以硝基取代的萘酰亚胺类化合物为前驱体,具有通式I的结构。该种方法可用于超临界CO-(2)中萘酰亚胺类染料的合成与染色,该种方法实现了荧光染料清洁化生产和染色方法的创新,为合理资源化利用超临界CO-(2)和减少染料合成与染色带来环境污染问题提供创新思想。(The invention discloses a naphthalimide dye containing amino in supercritical CO 2 The method of (1) synthesis and dyeing with supercritical carbon dioxide (CO) 2 ) As solvent, nitro-substituted naphthalimide compound as dye precursor, Au/TiO 2 As catalyst, H 2 As a reducing agent, the supercritical CO is realized under different temperature, pressure and time conditions 2 A method for synchronizing the synthesis of the fluorescent dye of the medium naphthalimide and the dyeing of textiles. The nitro-substituted naphthalimide compound is used as a precursorThe body has a structure of formula I. The method can be used for supercritical CO 2 The method realizes the clean production of fluorescent dye and the innovation of a dyeing method, and realizes the reasonable resource utilization of supercritical CO 2 And the problem of environmental pollution caused by dye synthesis and dyeing is reduced, and an innovative idea is provided.)

1. Naphthalimide dyes containing amino in supercritical CO₂The synthesis method is characterized in that supercritical carbon dioxide is used as a solvent, nitro-substituted naphthalimide compounds are used as dye precursors, Au/TiO₂As catalyst, H₂As a reducing agent, synthesizing a naphthalimide fluorescent dye containing amino; the precursor of the nitro-substituted naphthalimide compound has a structure of a general formula I:

in formula I:

R₁selected from H or R₄；

One of (1);

wherein the content of the first and second substances,

n is an integer of 1-6;

x is C or N;

y is NH, S or O;

R₅is H, CH₃，OCH₃F, Cl, Br or I;

R₂and R₃Independently selected from H, NO₂，NH₂Or NHCOCH₃And R is₂And R₃At least one of them being NO₂。

2. The method for dyeing a naphthalimide-based dye having an amino group according to claim 1, wherein a dyed fabric is obtained by dyeing a fabric to be dyed while synthesizing a naphthalimide-based fluorescent dye having an amino group.

3. The method of claim 2, comprising the steps of: sequentially putting a dye precursor, a catalyst and a fabric to be dyed into supercritical CO₂In the reaction kettle, H is introduced₂As a reducing agent, CO is introduced₂And (2) as a reaction and dyeing medium, adding or not adding an organic solvent at the same time, starting a heating system to increase the temperature of the system, starting a pressurizing system to increase the pressure of the system, when the temperature is increased to the reaction temperature and the pressure is increased to the reaction pressure, reacting under the conditions to realize the synchronous synthesis and dyeing of the dye, releasing the pressure and cooling to a normal state after the reaction and dyeing are finished to obtain a dyed fabric, and recovering the residual dye.

4. The method according to claim 1 or 2, wherein the loading amount of Au in the catalyst is 0.5-2.5 wt%; the particle size of the Au nano particles is 1-15 mu m.

5. The method of claim 1 or 2, wherein H is₂The pressure is 0.1-10 MPa.

6. The method according to claim 1 or 2, characterized in that the conditions for dye synthesis and dyeing are: the temperature is 40-200 ℃, the reaction pressure is 8-35 MPa, and the reaction time is 0.1-48 hours.

7. The method according to claim 1, 2 or 3, characterized in that during the dye synthesis and dyeing, an organic solvent is added or not added, wherein the organic solvent is N-methyl pyrrolidone, N-dimethylformamide or ethylene glycol monomethyl ether; the ratio of the dye precursor to the organic solvent is 0.05-5 g: 0-10.0 mL.

8. A method according to claim 1, 2 or 3, wherein the dye precursor is reacted with Au/TiO₂The mass ratio of the catalyst is 1:0.5, and the mass ratio of the dye precursor to the fabric to be dyed is 1: 50-1: 100.

9. A method according to claim 2 or 3, characterized in that the fabric to be dyed is a natural or chemical fabric.

10. For supercritical CO₂A composition for dyeing fabrics, comprising the amino group-containing naphthoimide-based dye according to claim 1.

Technical Field

The invention belongs to the technical field of textile printing and dyeing, and relates to supercritical CO₂Waterless dyeing technology and supercritical CO₂The synthesis reaction technology.

Background

Supercritical CO₂The fluid has relatively mild critical condition (T)_C＝31.1℃，P_C7.38MPa), has a plurality of beneficial properties of stable property, low price, innocuity, incombustibility, recyclability and the like, thereby becoming a commercial and industrial solvent with important application value and being widely developed and applied as a green substitute medium for natural product extraction, organic chemical reaction and textile dyeing.

Supercritical CO₂The waterless dyeing technology has been widely developed since the first use by Schollmeyer in the textile field in 1988. By using supercritical CO₂The fluid is superior to conventional water dyeing as dyeing medium, and has high dye utilization rate, short dyeing time, no sewage discharge to environment, dye and CO₂Can be recycled and the like. Meets the requirements of clean production, energy conservation and emission reduction at present,The research concept of environmental protection. Many efforts have been made to dye synthetic fibers, especially polyester dyes, using disperse dyes. However, there are few reports of the introduction of fluorescent disperse dyes into this new staining technique.

At present, can be suitable for supercritical CO₂The fluid dyeing fluorescent dyes are not many in variety, and mainly comprise two types of low-polarity micromolecular fluorescent dyes, namely naphthalimide derivatives and 1, 8-naphthalimide derivatives. The naphthalimide compound has a typical Intramolecular Charge Transfer (ICT) structure, the fluorescence performance of the naphthalimide compound is mainly influenced by an electron donating group and an electron withdrawing group on a dye parent, and when the nitro group in the molecular structure of the dye is reduced into an amino group, the electron donating capability of the group can be improved, so that the emission wavelength of the dye is changed, and the photophysical performance is obviously enhanced. The traditional method for reducing nitro group into amino group mainly adopts a stannous chloride/hydrochloric acid system or a sodium sulfide system, but the system is easy to cause environmental pollution. Therefore, in order to obtain the naphthalimide fluorescent dye, the development of a green and pollution-free solvent system for the nitro reduction reaction has important research value.

Disclosure of Invention

Based on the research background, the invention provides a naphthalimide dye containing amino in supercritical CO₂The method of synthesizing and dyeing with supercritical CO₂Solvents for green synthesis of dyes based on Au/TiO₂The catalyst is used for catalyzing and reducing nitro to amino, and the precursor of the naphthalimide dye with nitro substitution is reduced to obtain the disperse fluorescent dye with high fluorescence quantum yield. Combined with supercritical CO₂Reaction and dyeing technique in supercritical CO₂The method realizes the innovation of clean production and dyeing method of the fluorescent dye and reasonably utilizes the supercritical CO as a resource₂And the problem of environmental pollution caused by dye synthesis and dyeing is reduced, and an innovative idea is provided.

In the first aspect of the invention, aiming at the defects of the existing naphthalimide dye nitro-reduction system, the invention modifies the dye synthesis system and provides a naphthalimide dye containing aminoBoundary CO₂In a medium synthesis process with supercritical carbon dioxide (CO)₂) As solvent, nitro-substituted naphthalimide compound as dye precursor, Au/TiO₂As catalyst, H₂The reaction is carried out under different temperature, pressure and time conditions as a reducing agent to reduce the nitro group into an amino group, so as to synthesize the naphthalimide fluorescent dye containing the amino group.

The precursor of the adopted nitro-substituted naphthalimide compound has the following structural general formula I:

in formula I:

R₁selected from H or R₄；

One of (1);

wherein the content of the first and second substances,

n is an integer of 1-6;

x is C or N;

y is NH, S or O;

R₅is H, CH₃，OCH₃F, Cl, Br or I.

R₂And R₃Independently selected from H, NO₂，NH₂Or NHCOCH₃And R is₂And R₃At least one of them being NO₂。

Specifically, when R is₂Is NO₂When R is₃Independently selected from H, NO₂，NH₂Or NHCOCH₃(ii) a The reaction formula is as follows:

when R is₃Is NO₂When R is₂Independently selected from H, NO₂，NH₂Or NHCOCH₃(ii) a The reaction formula is as follows:

in a second aspect of the present invention, there is provided the above method for dyeing a naphthalimide-based dye containing an amino group, wherein a fabric to be dyed is dyed while synthesizing a naphthalimide-based fluorescent dye containing an amino group, to obtain a dyed fabric. In the invention, supercritical CO is introduced₂The method is used as a reaction medium for dye synthesis and a dyeing medium for textiles, and realizes the synchronous synthesis and dyeing of the naphthalimide fluorescent dye. The synchronous dye synthesis and dyeing technology refers to supercritical CO₂In a reaction kettle, supercritical CO is added₂As reaction medium and dyeing medium, naphthalene imide dye precursor containing nitro group is used as raw material in Au/TiO₂Catalysis H₂Under the reducing condition, the synthesis of the nitro naphthalimide dye and the fabric dyeing are completed.

The precursor of the naphthalimide compound with the structural general formula I can be substituted by H₂Reducing to obtain fluorescent naphthalimide dyes, which can be used in chemical fabrics and natural fabrics in supercritical CO₂The dyeing in (1) is the application of the dye in the examples. The experimental result shows that the precursor compound is applied to supercritical CO₂Has good solubility, can be reduced into amino naphthalimide dye with high yield (80-90 percent), and simultaneously completes the dyeing of fabrics. And testing and analyzing the color fastness of the dyed fabric, and comprehensively evaluating the dyeing performance of the dye on the fabric.

In a third aspect of the invention, there is provided a method for supercritical CO₂A fabric dyeing composition comprising the amino group-containing naphthalimide-based dye.

The invention converts supercritical CO₂As a green reaction solvent, the method is applied to the synthesis research of disperse fluorescent dye suitable for the fluorescent dyeing of textile materials; at the same time, the supercriticalCO₂Reaction and supercritical CO₂The combination of anhydrous dyeing technology and supercritical CO₂In the medium, the synthesis of the disperse fluorescent dye and the dyeing of the fabric are synchronously realized. Effectively reduces the use of a large amount of toxic and harmful reagents in dye synthesis, and reduces the CO with greenhouse effect₂And recycling the gas. Therefore, the present invention is significant in terms of environment, energy, efficiency, and the like.

Drawings

FIG. 1 is a picture of a polyester fabric before and after the NP-NH synchronous dyeing in example 6 (no NMP is present in the reaction system), wherein a is a picture of an undyed polyester fabric, b is a picture of a dyed polyester fabric under sunlight, and c is a fluorescent picture of a dyed polyester fabric under an ultraviolet lamp;

FIG. 2 is a picture of a polyester fabric before and after the NP-NH synchronous dyeing in example 6 (NMP is present in the reaction system), wherein a is a picture of an undyed polyester fabric, b is a picture of a dyed polyester fabric under sunlight, and c is a fluorescent picture of a dyed polyester fabric under an ultraviolet lamp;

fig. 3 is a picture of the polyester fabric before and after the NH-dimethyl synchronous process dyeing in example 6 (no NMP is present in the reaction system), wherein a is a picture of the undyed polyester fabric, b is a picture of the dyed polyester fabric under sunlight, and c is a fluorescent picture of the dyed polyester fabric under an ultraviolet lamp.

Fig. 4 is a picture of the polyester fabric before and after the NH-dimethyl synchronous process dyeing in example 6 (NMP is present in the reaction system), wherein a is a picture of the undyed polyester fabric, b is a picture of the dyed polyester fabric under sunlight, and c is a fluorescent picture of the dyed polyester fabric under an ultraviolet lamp.

Detailed Description

Unless otherwise indicated, the terms used herein have the following meanings.

Naphthalimide dyes containing amino in supercritical CO₂The neutral synthesis and dyeing method uses supercritical carbon dioxide as solvent, nitro-substituted naphthalimide compound as dye precursor, Au/TiO₂As catalyst, H₂As reducing agents by reductionSynthesizing a naphthalimide fluorescent dye containing amino; the naphthalimide compound precursor containing amino has a structure shown in a general formula I:

in the compounds of the general formula I according to the invention, R₁Selected from H or R₄；

One of (1);

wherein the content of the first and second substances,

n is an integer of 1-6;

x is C or N;

y is NH, S or O;

R₅is H, CH₃，OCH₃F, Cl, Br or I;

R₂and R₃Independently selected from H, NO₂，NH₂And NHCOCH₃And R is₂And R₃At least one of them being NO₂。

The second aspect of the present invention provides a dyeing method of the above naphthalimide dyes containing amino groups, which comprises synthesizing a naphthalimide fluorescent dye containing amino groups, dyeing a fabric to be dyed to obtain a dyed fabric, and realizing supercritical CO₂A method for synchronizing the synthesis of the middle naphthalimide fluorescent dye and the dyeing of textiles; namely, taking supercritical carbon dioxide as a solvent, taking nitro-substituted naphthalimide compounds as a dye precursor, Au/TiO₂As catalyst, H₂As a reducing agent, a fabric to be dyed is dyed, and a naphthalimide fluorescent dye containing an amino group is synthesized, and the dyed fabric is obtained.

The naphthalimide dye containing amino is subjected to supercritical CO₂The method for synthesizing and dyeing specifically comprises the following steps:

sequentially adding dyesPrecursor compound, Au/TiO₂Catalyst and textile to be dyed (fabric to be dyed) are placed in supercritical CO₂In the reaction kettle, i.e. the dyeing device, H is introduced₂As a reducing agent, CO is introduced₂And (2) as a reaction and dyeing medium, simultaneously adding or not adding a small amount of organic solvent, starting a heating system to increase the temperature of the system, starting a pressurizing system to increase the pressure of the system, realizing the synchronous synthesis and dyeing of the dye under the condition when the temperature is increased to the reaction temperature and the pressure is increased to the reaction pressure, releasing the pressure to the normal pressure (0.10MPa) after the synthesis of the dye is finished after the reaction and dyeing for a certain time, cooling to the normal temperature (25 ℃) to obtain the dyed fabric, and recovering the residual dye.

In a preferred embodiment, the supported amount of Au in the catalyst is 0.5-2.5 wt%, preferably 1.61 wt%.

In a preferred embodiment, the particle size of the Au nanoparticles in the catalyst is in a range of 1-15 μm.

In a preferred embodiment, the dye precursor is reacted with Au/TiO₂The mass ratio of the catalyst is 1: 0.5-5: 1, and the mass ratio of the dye precursor to the textile (to-be-dyed fabric) to be dyed is 1: 50-1: 100.

In a preferred embodiment, H₂The pressure of the dye precursor is 0.1-10 MPa, the temperature of a synthesis and dyeing system is 40-200 ℃, the pressure of the synthesis and dyeing system is 10-30 MPa, the synthesis and dyeing time is 0.1-48 hours, a small amount of organic solvent is N-methylpyrrolidone (NMP), N-Dimethylformamide (DMF), Ethylene Glycol Monomethyl Ether (EGME), and the proportion of the dye precursor to the organic solvent is 0.05-5 g: 0-10.0 mL.

In a more preferred embodiment, H₂The pressure of the dye precursor is 0.5-5 MPa, the temperature of a synthesis and dyeing system is 80-150 ℃, the pressure of the synthesis and dyeing system is 15-28 MPa, the synthesis and dyeing time is 1-24 hours, a small amount of organic solvent is N-methylpyrrolidone (NMP) and N, N-Dimethylformamide (DMF), and the ratio of the dye precursor to the organic solvent is 0.05 g: 0-5.0 mL.

In the most preferred embodimentIn (H)₂The pressure of the dye precursor is 1-2.5 MPa, the temperature of a synthesis and dyeing system is 100-120 ℃, the pressure of the synthesis and dyeing system is 20-25 MPa, the synthesis and dyeing time is 3-12 hours, a small amount of organic solvent is N-methylpyrrolidone (NMP), and the ratio of the dye precursor to the organic solvent is 0.05 g: 0-2.5 mL.

In a preferred embodiment, the fabric is a natural fiber fabric (such as cotton fabric and wool fabric) or a chemical fiber fabric (such as polyester fabric and acrylic fabric).

In the above description of the precursors of the nitro-substituted naphthalimide compounds of the present invention, the definitions and preferences of the substituents are the same as those in the description of the compounds of the present invention.

The naphthalimide dye compound synthesized by the method adopts a nuclear magnetic resonance spectrogram or a mass spectrum to confirm the structure, and is assisted with carbon spectrum and mass spectrum tests to confirm the structure.

The invention relates to supercritical CO₂The method for synthesizing and dyeing the naphthalimide dye synchronously has the following characteristics:

the synchronous synthesis and dyeing method combines supercritical CO₂The reaction and dyeing technology reduces the use of toxic and harmful reagents in dye synthesis and uses CO₂The gas is recycled, and the method is green and clean.

These and other features and advantages of the present invention will be apparent upon reference to the following detailed description.

In view of the above, the naphthalimide fluorescent dye can be used in supercritical CO₂The synthesis and dyeing are carried out.

Example 1

Au/TiO₂Synthesis of (2)

0.01g of tetrachloroauric acid was weighed and dissolved in 10mL of deionized water to obtain a pale yellow transparent liquid. Then, the pH was adjusted to neutral by using a 1mol/L NaOH aqueous solution, and the solution gradually became colorless. 0.13g of mesoporous TiO is weighed₂Adding into the solution, stirring at room temperature for 4 hr to obtain milky solutionAnd (4) color. After the reaction was completed, the reaction solution was filtered and washed with ice water, and the filter cake was silver gray. The filter cake was dried overnight in an oven at 50 ℃ and the filter cake turned purple. Finally, the filter cake is placed in a beaker and baked for 3 hours in an oven at the high temperature of 250 ℃ to obtain Au/TiO₂The catalyst is purple black solid powder.

Example 2

Preparation of Naphthylimide dye Compound NP-NH (without addition of organic solvent NMP)

Adding 3-nitro-1, 8-naphthalic anhydride (0.20g, 0.82mmol) into 15mL of ammonia water, stirring overnight at room temperature, pouring the reaction solution into ice water after the reaction is finished to separate out solid, filtering, washing and drying to obtain a precursor compound 3-nitro-1, 8-naphthalimide (NO-NH) (0.18g, 0.74mmol) which is white solid powder and directly carrying out the next step without purification.

The compound NO-NH (0.20g, 0.83mmol) and 0.05g Au/TiO₂The catalyst is placed in a reaction kettle, the reaction kettle is sealed, and 1.9MPa H is introduced₂Then introducing 6.4MPa CO₂Regulating CO₂And H₂The pressure of the system is 20MPa, and the temperature in the kettle is adjusted to 120 ℃. Stirring for reaction for 3h, discharging gas, standing the reaction kettle, cooling to normal state, and adding CH₃Dissolving the product in OH, filtering, washing the upper layer solid to obtain catalyst, reduced pressure rotary steaming to obtain disperse fluorescent dye 3-amido-1, 8-naphthalimide (NP-NH) (0.15g, 0.70mmol), and separating by column chromatography to obtain pure product (CH)₃OH/CH₂Cl₂1:500-2:500) in 85% yield.¹H NMR(400MHz,DMSO-d₆)δ11.53(s,1H),8.04(s,1H),8.02(s,1H),7.91(d,J＝2.4Hz,1H),7.61(t,J＝7.8Hz,1H),7.28(d,J＝2.3Hz,1H),5.97(s,2H)。¹³C NMR(100MHz,DMSO-d₆) δ 164.97,164.71,148.19,134.31,131.99,127.28,125.14,123.53,122.71,122.31,121.52,112.21. NP-NH formula is C₁₂H₈N₂O₂Molecular weight 212.2, MS hairThe molecular weight of (M-1) was found to be 211.1.

Example 3

Preparation of the Naphthylimide dye Compound NP-NH (addition of organic solvent NMP)

(1) Synthesis of precursor NP-NO

Raw materials, amounts and operations were as in example 2.

(2) Synthesis of fluorescent dye NP-NH (adding organic solvent NMP)

The compound NO-NH (0.20g, 0.83mmol), 0.05g Au/TiO₂The catalyst and 0.5mL of NMP are placed in a reaction kettle, the reaction kettle is sealed, and 1.9MPa of H is introduced₂Then introducing 6.4MPa CO₂Regulating CO₂And H₂The pressure of the system is 20MPa, and the temperature in the kettle is adjusted to 120 ℃. Stirring for reaction for 3h, discharging gas, standing the reaction kettle, cooling to normal state, and adding CH₃Dissolving the product in OH, filtering, washing the upper layer solid to obtain catalyst, reduced pressure rotary steaming to obtain disperse fluorescent dye 3-amido-1, 8-naphthalimide (NP-NH) (0.15g, 0.70mmol), and separating by column chromatography to obtain pure product (CH)₃OH/CH₂Cl₂1:500-2:500) in 85% yield.

Example 4

Preparation of the Naphthylimide dye Compound NP-dimethyl (without addition of organic solvent NMP)

3-Nitro-1, 8-naphthalic anhydride (0.20g, 0.82mmol) was added to 9mL CH₃In COOH, heating and dissolving, the solution is milky white, after 3-nitro-1, 8-naphthalic anhydride is completely dissolved, 1mL of 2, 4-dimethylaniline is added into the reaction system, the solution is light red, the solution is heated to 115 ℃ and reflows for reaction for 8h, after the reaction is finished, the mixture is poured into ice water, solid is separated out, and the wine red product N- (2, 4-dimethyl) phenyl-3-nitro-1, 8-naphthalimide (NO-dimethyl) (0.94g, 2.70mmol) is obtained by filtering, washing and drying, and the next step is directly carried out without purification.

The compound NO-dimethyl (0.20g, 0.5)8mmol) and 0.05g Au/TiO₂The catalyst is placed in a reaction kettle, and after the reaction kettle is sealed, H is firstly introduced at the pressure of 1.9MPa₂Then introducing CO at the pressure of 6.4MPa₂The temperature in the reaction kettle is controlled to be 120 ℃ and the pressure is controlled to be 20 MPa. After reacting for 3h, gas is discharged, the reaction kettle is kept stand and cooled, and CH is used₃OH dissolving the product, filtering, washing to obtain catalyst, reduced pressure rotary steaming to obtain disperse fluorescent dye N- (2, 4-dimethyl) phenyl-3-amido-1, 8-naphthalimide (NP-dimethyl) (0.15g, 0.48mmol), and separating by column chromatography to obtain pure product (CH)₃OH/CH₂Cl₂1:500-2:500), yield 82.8%.¹H NMR(400MHz,DMSO-d₆)δ8.11(d,J＝2.6Hz,1H),8.09(d,J＝1.4Hz,1H),8.00(d,J＝2.2Hz,1H),7.66(t,J＝7.8Hz,1H),7.35(d,J＝2.3Hz,1H),7.20(s,1H),7.18–7.09(m,2H),2.36(s,3H),2.00(s,3H)。¹³C NMR(100MHz,DMSO-d₆) δ 164.15,163.96,148.38,138.14,135.65,134.21,133.16,132.20,131.43,129.33,127.64,127.47,126.07,123.27,122.49,122.33,121.57,112.42,21.15, 17.48. NP-NH formula is C₂₀H₁₆N₂O₂Molecular weight 316.35, MS found its (M-1) molecular weight 317.1.

Example 5

Preparation of the Naphthylimide dye Compound NP-dimethyl (addition of organic solvent NMP)

(1) Synthesis of precursor NO-dimethyl

Raw materials, amounts and operations were as in example 4.

(2) Synthesis of fluorescent dye NP-dimethyl (adding organic solvent NMP)

The compound NO-dimethyl (0.20g, 0.58mmol), 0.05g Au/TiO₂Catalyst and 0.5mL NMP are placed in a reaction kettle, and after the reaction kettle is closed, H is firstly introduced at the pressure of 1.9MPa₂Then introducing CO at the pressure of 6.4MPa₂The temperature in the reaction kettle is controlled to be 120 ℃ and the pressure is controlled to be 20 MPa. After reacting for 3h, gas is discharged, the reaction kettle is kept stand and cooled, and CH is used₃OH dissolving the product, filtering, washing to obtain a catalyst, and carrying out reduced pressure rotary evaporation to obtain the disperse fluorescent dye N- (2, 4-dimethyl) phenyl-3-amido-1, 8-naphthalimideAmine (NP-dimethyl) (0.15g, 0.48mmol), and separating by column chromatography to obtain pure product (CH)₃OH/CH₂Cl₂1:500-2:500), yield 82.8%.

Example 6

Supercritical CO₂Method for synchronizing dye synthesis and dyeing in medium

The dyeing experiment is carried out in supercritical CO₂In the medium, the synthesis of dyes NP-NH and NP-dimethyl is combined with the dyeing, the NO-NH and NO-dimethyl respectively synthesized in the embodiment 2 and the embodiment 3 are adopted as fluorescent dye precursors, and the Au/TiO synthesized in the embodiment 1 is adopted₂Directly placing catalyst in a reaction kettle, wherein the reaction kettle is a mini reaction kettle/REACTOR (WZC-100-HP) developed by Wuzhou Dingchu (Beijing) science and technology limited, cutting two blocks into 4cm × 10cm × 0.01cm terylene fabrics, hanging in the mini reaction kettle, introducing H₂As a reducing agent, CO is introduced₂As a reaction and dyeing medium, dye synthesis and dyeing are carried out simultaneously. The conditions of dye synthesis and dyeing are that the pressure is 20MPa, the temperature is 120 ℃, and the time is 3H (H is introduced under the pressure of 1.9MPa₂Then introducing CO at the pressure of 6.4MPa₂Controlling the temperature in the reaction kettle at 120 ℃ and the pressure at 20MPa, and reacting for 3 hours). The amounts of the starting materials and other operations were as described in examples 2 to 5. The polyester fabrics dyed by NP-NH and NP-dimethyl are subjected to soaping color fastness, friction color fastness and light color fastness tests, and the test data are respectively shown in the table 1 and the table 2.

TABLE 1 soaping color fastness, rubbing color fastness and light color fastness of the NP-NH dyed polyester fabrics

TABLE 2 soaping color fastness, rubbing color fastness and light color fastness of the NP-dimethyl dyed polyester fabrics

The above description is only an embodiment of the present invention, but the scope of the present invention is not limited to the above embodiments, and any person skilled in the art can be covered within the scope of the present invention without any changes or substitutions that may occur to those skilled in the art without departing from the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope defined by the claims.