KR102174800B1 - Anthraquinone based dyes for supercritical fluid dyeing and Supercritical fluid dyeing of polyester fabrics using the same - Google Patents

Abstract

The present invention relates to a novel anthraquinone dye for supercritical fluid dyeing and a supercritical fluid dyeing method of polyester fiber using the same, wherein the anthraquinone dye is a blue hydrophobic disperse dye and has excellent solubility in supercritical fluid. It is commercially acceptable and exhibits practically satisfactory color uniformity, making it usable as a dye for supercritical fluid dyeing.

Description

Anthraquinone based dyes for supercritical fluid dyeing and Supercritical 　fluid dyeing of polyester fabrics using the same}

The present invention relates to a novel anthraquinone dye for supercritical fluid dyeing and a supercritical fluid dyeing method of polyester fiber using the same.

The dyeing process in the textile industry is mainly performed by a wet dyeing method. The use of a large amount of water is required for dyeing polyester fibers, and chemical additives such as dispersants and surfactants are required to improve the solubility of the dye in water.

However, such a wet dyeing method discharges a huge amount of wastewater and requires a separate post-treatment process to purify the discharged wastewater, and thus has an economic problem as well as an environmental problem.

Accordingly, the burden of companies on dyeing wastewater treatment is increasing due to increased awareness of environmental pollution and strengthening of regulations, and development of a new clean dyeing process technology that can fundamentally reduce dyeing wastewater itself is required.

Many efforts to solve the problems of the wet process are being studied in various approaches, and among them, the dry dyeing process using a supercritical fluid is being studied as an alternative.

Recently, as global brands such as Nike and Adidas have launched clothing products using supercritical fluid dyeing, interest in supercritical fluid dyeing is increasing worldwide.

In 1991, Schollmeyer et al. announced a technology for dyeing fibers after dissolving dyes in supercritical carbon dioxide, and DyeCoo of the Netherlands, which successfully commercialized a supercritical fluid dyeing machine from 2011, and Huntsman of Germany, a dye maker, made a business partnership. By promoting the development of dyes for textile dyeing using 100% PET and Spandex, we developed commercial dispersion dyes capable of dyeing textile materials, which are pure dyes that do not contain any surfactants, unlike the current dispersion dyes dyed in water. have.

On the other hand, dyes for dyeing supercritical fluids have been partially developed by Huntsman and Colourtex, India, and are limitedly supplied, but there is little development of dyes for dyeing supercritical fluids in Korea.

Therefore, there is a need to develop various dyes that can be used in a supercritical fluid dyeing process.

U.S. Patent 8,409,300 U.S. Patent 9,376,570

The present invention provides an anthraquinone compound that can be used as a dye for supercritical fluid dyeing.

In addition, the present invention provides a method of dyeing a polyester fiber with a supercritical fluid using the anthraquinone compound as a dye.

The present invention provides an anthraquinone compound that can be used as a dye for supercritical fluid dyeing, and the anthraquinone compound may be represented by the following Formula 1 or Formula 2:

[Formula 1]

[Formula 2]

(In Formulas 1 and 2,

R ₁ , R ₂ and R ₃ are each independently hydrogen, C1-C20 alkyl or -(OL) _a -R', provided that R ₁ is C1-C20 alkyl or -(OL) _a -R' ₂ and R ₃ are both hydrogen, and when R ₁ is hydrogen, R ₂ and R ₃ are each independently C1-C20 alkyl or -(OL) _a -R';

L is C1-C20 alkylene; a is an integer from 0 to 10; R'is C1-C20 alkyl or C1-C20 alkoxy;

R ₄ is C1-C20 alkyl; R ₅ is hydrogen, C1-C20 alkyl or C1-C20 alkoxy; m is an integer from 1 to 5.)

The anthraquinone compound according to an embodiment of the present invention may be represented by the following Formula 3, Formula 4, or Formula 5:

[Formula 3]

[Formula 4]

[Formula 5]

(In Chemical Formulas 3 to 5,

R ₁ is C1-C20 alkyl or -(OL) _a -R'; L is C1-C20 alkylene; a is an integer from 1 to 10; R'is C1-C20 alkoxy;

R ₂ is C1-C20 alkoxy; R ₃ is C1-C20 alkyl;

R ₄ is C1-C20 alkyl.)

In the anthraquinone compound of Formulas 3 to 5 according to an embodiment of the present invention, R ₁ is C1-C10 alkyl or -(OL) _a -R', L is C1-C10 alkylene, and a is 1 Is an integer of 5, R'is C1-C10 alkoxy, R ₂ is C1-C10 alkoxy, R ₃ is C1-C10 alkyl, and R ₄ may be C7-C20 alkyl.

In the anthraquinone compound of Formulas 3 to 5 according to an embodiment of the present invention, R ₁ is C1-C7 alkyl or -(OL) _a -R', L is C2-C5 alkylene, and a is 1 Is an integer of 3, R′ is C1-C7 alkoxy, R ₂ is C1-C7 alkoxy, R ₃ is C1-C7 alkyl, and R ₄ may be C7-C20 alkyl.

The anthraquinone compound according to an embodiment of the present invention may be any one selected from the following structures.

In addition, the present invention provides a method of dyeing a polyester fiber with a supercritical fluid using the anthraquinone compound as a dye.

In the supercritical fluid dyeing method of polyester fiber according to an embodiment of the present invention, the supercritical fluid may be supercritical carbon dioxide.

In the supercritical fluid dyeing method of a polyester fiber according to an embodiment of the present invention, when dyeing the supercritical fluid, the dyeing temperature may be 80 to 120 °C, and the dyeing pressure may be 5 to 15 MPa.

The anthraquinone compound according to the present invention is a blue hydrophobic disperse dye, has excellent solubility in a supercritical fluid, is commercially acceptable, and exhibits practically satisfactory color uniformity, making it a hydrophobic disperse dye for a supercritical fluid dyeing process. Can be used.

Due to the solubility properties of the anthraquinone compound and the fast diffusion rate, the anthraquinone compound as a dispersing dye is directly dissolved in the supercritical fluid without a separate dispersant, and quickly penetrates and adsorbs onto the polyester fiber, thus having excellent dyeing and fastness properties. Supercritical fluid dyed polyester fibers can be obtained.

In addition, when dyeing a polyester fiber with a supercritical fluid using the anthraquinone compound according to the present invention as a dispersing dye, a supercritical fluid, especially supercritical carbon dioxide, is used as a dyeing solvent, so unlike the conventional wet dyeing process, water and a dispersant Do not use at all. Therefore, there is an advantage of being able to omit the wastewater treatment process and the drying process essential in the existing wet dyeing process.

In addition, it is possible to recover and recycle the anthraquinone dye that is not dyed and dissolved in the supercritical fluid after dyeing, and the used carbon dioxide can also be recycled by the recycling process design, so it is environmentally friendly.

Therefore, the supercritical fluid dyeing method of polyester fibers using an anthraquinone compound as a disperse dye according to the present invention is not only environmentally friendly, but also economical because it can reduce production costs.

1 is a graph showing the change in color intensity (K/S) of a supercritical dyed polyester fabric according to dye concentration, (b) dyeing temperature and (c) dyeing pressure.
2 is a graph showing a change in color intensity (K/S) of a supercritical dyed polyester fabric according to a dyeing temperature.
3 is a graph showing a change in color intensity (K/S) of a supercritical dyed polyester fabric according to dyeing pressure.
4 is a photograph of a supercritical dyed polyester fabric.
5 is a graph showing the color intensity (K/S) and fixation rate (F) values of the supercritical dyed polyester fabric.

Hereinafter, the present invention will be described in more detail. If there are no other definitions in the technical and scientific terms used at this time, they have the meanings commonly understood by those of ordinary skill in the technical field to which this invention belongs, and the following description will unnecessarily obscure the subject matter of the present invention. Description of possible known functions and configurations will be omitted.

As used herein, the term “alkyl” refers to a monovalent straight chain or branched saturated hydrocarbon group consisting of only carbon and hydrogen atoms, and “alkoxy” refers to a monovalent group having a bonding position to oxygen and an alkyl bonded to oxygen, “Alkylene” means a divalent group in which two hydrogen atoms have been removed from a straight chain or branched saturated hydrocarbon.

One aspect of the present invention provides an anthraquinone compound that can be used as a hydrophobic disperse dye in a supercritical fluid dyeing process. The anthraquinone compound of the present invention is commercially acceptable and exhibits practically satisfactory color uniformity and can be used as a dye for fibers.

In one embodiment of the present invention, the anthraquinone compound may be represented by Formula 1:

[Formula 1]

(In Formula 1,

R ₁ , R ₂ and R ₃ are each independently hydrogen, C1-C20 alkyl or -(OL) _a -R', provided that R ₁ is C1-C20 alkyl or -(OL) _a -R' ₂ and R ₃ are both hydrogen, and when R ₁ is hydrogen, R ₂ and R ₃ are each independently C1-C20 alkyl or -(OL) _a -R';

L is C1-C20 alkylene;

R'is C1-C20 alkyl or C1-C20 alkoxy;

a is an integer from 0 to 10.)

In terms of having excellent solubility in a supercritical fluid, specifically, the anthraquinone compound of Formula 1 may be represented by the following Formula 3 or Formula 4:

[Formula 3]

[Formula 4]

(In Chemical Formulas 3 and 4,

R ₁ is C1-C20 alkyl or -(OL) _a -R';

L is C1-C20 alkylene;

R'is C1-C20 alkoxy;

R ₂ is C1-C20 alkoxy;

R ₃ is C1-C20 alkyl;

a is an integer from 1 to 10.)

And (OL) _a -R ', - on the second side to have a supercritical fluid when dyed excellent dyeability of the polyester fiber, wherein the anthraquinone compound of formula (3) or formula (4), preferably wherein R ₁ is C1-C10 alkyl, L is C1-C10 alkylene, R'is C1-C10 alkoxy, R ₂ is C1-C10 alkoxy, R ₃ is C1-C10 alkyl, and a may be an integer of 1 to 5.

More preferably, the anthraquinone compound of Formula 3 or Formula 4, wherein R ₁ is C1-C7 alkyl or -(OL) _a -R', L is C2-C5 alkylene, and R'is C1-C7 Alkoxy, R ₂ is C1-C7 alkoxy, R ₃ is C1-C7 alkyl, and a may be an integer of 1 to 3.

In the anthraquinone compounds of Formulas 3 and 4 according to an embodiment of the present invention, R ₁ is C3-C7 alkyl or -(OL) _a -R', L is C2-C3 alkylene, and a is 1 To 2 is an integer, R'is C1-C3 alkoxy, R ₂ is C1-C3 alkoxy, and R ₃ may be C1-C3 alkyl.

In one embodiment of the present invention, the anthraquinone compound may be represented by Formula 2:

[Formula 2]

(In Chemical Formula 2,

R ₄ is C1-C20 alkyl;

R ₅ is hydrogen, C1-C20 alkyl or C1-C20 alkoxy;

m is an integer from 1 to 5.)

In terms of having excellent solubility in a supercritical fluid, specifically, the anthraquinone compound of Formula 2 may be represented by the following Formula 5:

[Formula 5]

(In Formula 5, R ₄ is C1-C20 alkyl.)

In the second aspect for critical fluid dyeing have a good dyeability of a polyester fiber, an anthraquinone compound of the formula 5, preferably the R ₄ can be C7-C20 alkyl, the more preferably C7-C16 alkyl.

In one embodiment of the present invention, the anthraquinone compound may be more specifically selected from the following structures, but is not limited thereto.

The anthraquinone compound according to an embodiment of the present invention is a blue hydrophobic disperse dye, and has excellent solubility in a supercritical fluid.

Another aspect of the present invention provides a method of preparing the anthraquinone compound.

The anthraquinone compound according to an embodiment of the present invention may be prepared as shown in Schemes 1 and 2 below. Further details are described in Examples 1 to 9 below. However, the preparation method of the anthraquinone compound of the present invention is not limited to the following Reaction Schemes 1 or 2, and can be synthesized by various methods recognized by those skilled in the art using known organic reactions.

[Scheme 1]

(In Reaction Scheme 1, R ₁ , R ₂ and R ₃ are the same as defined in Formula 1.)

[Scheme 2]

(In Reaction Scheme 2, R ₄ , R ₅ and m are the same as defined in Formula 2.)

In one embodiment, the anthraquinone compound of Formula 1 is an aniline compound (R-1) using 1,8-dihydroxy-4,5-dinitroanthracene-9,10-dione as a starting material, and It can be prepared by condensation reaction.

In one embodiment, the aniline compound (R-1) may be used in 1 to 3 moles, preferably 1.5 to 2.5 moles, and more preferably 2 moles per 1 mole of the starting material.

In one embodiment, the anthraquinone compound of Formula 1 is a starting material of 1,8-dihydroxy-4,5-dinitroanthracene-9,10-dione in the presence of 2-methoxyethanol under reflux temperature. It can be prepared by condensation reaction with an aniline compound (R-1).

In one embodiment, the anthraquinone compound of Formula 2 is condensed with an amine compound (R-2) after preparing compound a by reacting 1,4-dihydroxyanthracene-9,10-dione with tosyl chloride Reaction to prepare compound b, and may be prepared by condensation reaction of compound b with benzylamine compound (R-3).

In one embodiment, the amine compound (R-2) may be used in an amount of 1 to 1.5 moles, preferably 1.1 to 1.3 moles per 1 mole of compound a, and the benzylamine compound (R-3) is 1 per 1 mole of compound b To 1.5 moles.

In one embodiment, the anthraquinone compound of Formula 2 is prepared by refluxing 1,4-dihydroxyanthracene-9,10-dione with tosyl chloride in the presence of triethylamine (Et ₃ N) to prepare compound a. Then, it may be prepared by condensation reaction with an amine compound (R-2) to prepare compound b, and a condensation reaction of compound b with a benzylamine compound (R-3) at reflux temperature in the presence of pyridine.

In one embodiment, the condensation reaction between the nitro (-NO ₂ ) group or tosyloxy (-OTs) group and the amino (-NH ₂ ) group of the reactant may be performed under various conditions that can be recognized by those skilled in the art. Of course.

The temperature of the condensation reaction according to an embodiment may be 100 to 140°C, preferably 120 to 130°C in terms of reaction efficiency, and the pH of the reaction mixture is 5 to 9, preferably 7 to 8 in terms of reaction efficiency. Can be

Another aspect of the present invention provides a method for dyeing a polyester fiber (PET, polyester fabric) with a supercritical fluid using the anthraquinone compound as a hydrophobic disperse dye.

Since the anthraquinone compound has hydrophobicity, it has excellent solubility in supercritical fluids. Due to the solubility properties of the anthraquinone compound and a fast diffusion rate, the anthraquinone compound as a dispersing dye can be dissolved directly in a supercritical fluid and rapidly penetrated and adsorbed onto the polyester fiber. Therefore, it is possible to obtain a supercritical fluid dyed polyester fiber having excellent dyeing properties and fastness properties by using the anthraquinone compound.

In addition, the supercritical fluid dyeing process using the anthraquinone compound as a dye uses a supercritical fluid as a solvent for dissolving the anthraquinone dye, so there is no wastewater treatment process because it does not use water at all before and after the dyeing process. , It is environmentally friendly because it is possible to recover and recycle the anthraquinone dye dissolved in the supercritical fluid without dyeing after dyeing.

In the supercritical fluid dyeing method according to an embodiment, the supercritical fluid may be supercritical carbon dioxide (CO2) having a strong hydrophobic property. The supercritical carbon dioxide is carbon dioxide in a state exceeding the critical temperature (31 °C) and the critical pressure (7.5 MPa), and refers to a fluid having both gas and liquid properties.

Since the polyester fiber is easily swelled in the supercritical carbon dioxide, the anthraquinone dye dissolved in the supercritical carbon dioxide can be more rapidly adsorbed and penetrated into the surface and inside of the swollen polyester fiber to be dyed.

In the supercritical fluid dyeing method according to an embodiment, the dyeing temperature is 80 to 150 °C, preferably in the range of 80 to 120 °C in terms of having excellent dyeing properties, the dyeing pressure is 5 to 20 MPa, excellent dyeing property In terms of having, it may be preferably in the range of 5 to 15 MPa.

Hereinafter, for a detailed understanding of the present invention, the representative compounds of the present invention will be described in detail by way of examples, and examples according to the present invention may be modified in various different forms, and the scope of the present invention is It should not be construed as being limited to the above-described embodiments. The embodiments of the present invention are provided to more completely describe the present invention to those of ordinary skill in the art.

All reagents and solvents were analytical grade, were used without further purification, and the structure of the synthesized anthraquinone compound was ¹ H NMR and ¹³ C NMR (AVANCE III spectroscopy, ¹ H NMR 600 MHz, ¹³ C NMR 150 MHz), It was confirmed by UV-Vis spectra (Agilent 8453 spectrophotometer) and HRMS (High resolution mass spectra, Bruker micrOTOF-Q spectrometer). The reflection spectra were recorded using a Shimadz UV 26000 spectrophotometer.

Preparation of anthraquinone compound

[Example 1] Preparation of anthraquinone compound (1)

1,8-dihydroxy-4,5-dinitroanthracene-9,10-dione (1,8-dihydroxy-4,5-dinitroanthracene-9,10-dione, 0.5 g, 1.514 mmol) at room temperature Was dissolved in 2-methoxyethanol (10 mL), and then 4-hexylaniline (4-Hexylaniline, 3.028 mmol) was added, followed by stirring at 125° C. for 6 hours. Then, the obtained crude product was purified by silica gel (230-400 mesh) column chromatography (eluent, 12-15% ethyl acetate: n-hexane) to obtain an anthraquinone compound (1) as a blue solid.

1-((4-Hexylphenyl)amino)-4,5-dihydroxy-8-nitroanthracene-9,10-dione (1): Blue solid; Yield: 86% (0.43 g); mp 115-117 °C; ¹ H NMR (CDCl ₃ , 600 MHz) δ 12.82 (s, 1H), 12.73 (s, 1H), 11.65 (s, 1H), 7.53 (d, J = 8.8 Hz, 1H), 7.48 (d, J = 9.7 Hz, 1H), 7.20 (d, J = 9.0 Hz, 1H), 7.14 (d, J = 8.0 Hz, 2H), 7.09 (d, J = 9.5 Hz, 1H), 7.05 (d, J = 8.0 Hz , 2H), 2.55 (t, J = 7.9 Hz, 2H), 1.55 (qt, J = 7.1 Hz, 2H), 1.32-1.21 (m, 8H), 0.83 (t, J = 6.7 Hz, 3H); ¹³ C NMR (CDCl ₃ , 150 MHz) δ 188.2, 176.4, 162.3, 157.9, 145.2, 141.0, 140.3, 134.3, 129.4, 128.6, 128.0, 127.2, 125.6, 123.8, 121.3, 114.5, 111.0, 107.3, 34.4, 30.6 , 30.3, 27.9, 21.5, 13.0; HRMS: 459.1522 [MH] ⁺ Calcd for C ₂₆ H ₂₃ N ₂ O ₆ : 459.1556.

[Example 2] Preparation of anthraquinone compound (2)

The reaction was carried out in the same manner as in Example 1, except that 4-pentylaniline (3.028 mmol) was used instead of 4-hexylaniline to obtain an anthraquinone compound (2) as a blue solid.

1,8-Dihydroxy-4-nitro-5-((4-pentylphenyl)amino)anthracene-9,10-dione (2): Blue solid; Yield: 84% (0.41 g); mp 260-262 °C; ¹ H NMR (CDCl ₃ , 600 MHz) δ 12.83 (s, 1H), 12.74 (s, 1H), 11.66 (s, 1H), 7.54 (d, J = 9.0 Hz, 1H), 7.49 (d, J = 9.5 Hz, 1H), 7.21 (d, J = 8.8 Hz, 1H), 7.15 (d, J = 8.2 Hz, 2H), 7.10 (d, J = 9.5 Hz, 1H), 7.06 (d, J = 8.2 Hz , 2H), 2.55 (t, J = 7.9 Hz, 2H), 1.56 (qt, J = 7.5 Hz, 2H), 1.32-1.23 (m, 4H), 0.84 (t, J = 6.9 Hz, 3H); ¹³ C NMR (CDCl ₃ , 150 MHz) δ 189.3, 177.5, 163.3, 158.9, 146.3, 142.1, 141.3, 135.3, 130.5, 129.6, 128.2, 126.7, 124.8, 122.3, 115.6, 112.1, 108.4, 35.4, 31.4, 31.0 , 22.5, 14.0; HRMS: 447.2458 [M+H] ^{+ Calcd} for C ₂₅ H ₂₃ N ₂ O ₆ : 447.4677.

[Example 3] Preparation of anthraquinone compound (3)

Except for using 4-butylaniline (4-Butylaniline, 3.028 mmol) instead of 4-hexylaniline, the reaction was carried out in the same manner as in Example 1 to obtain an anthraquinone compound (3) as a blue solid.

1-((4-Butylphenyl)amino)-4,5-dihydroxy-8-nitroanthracene-9,10-dione (3): Blue solid; Yield: 83% (0.39 g); mp 250-252 °C; ¹ H NMR (CDCl ₃ , 600 MHz) δ 12.83 (s, 1H), 12.74 (s, 1H), 11.66 (s, 1H), 7.54 (d, J = 8.8 Hz, 1H), 7.49 (d, J = 9.7 Hz, 1H), 7.20 (d, J = 8.8 Hz, 1H), 7.15 (d, J = 8.0 Hz, 2H), 7.10 (d, J = 9.7 Hz, 1H), 7.06 (d, J = 8.0 Hz , 2H), 2.56 (t, J = 7.7 Hz, 2H), 1.54 (qt, J = 7.7 Hz, 2H), 1.35-1.26 (m, 2H), 0.88 (t, J = 7.5 Hz, 3H); ¹³ C NMR (CDCl ₃ , 150 MHz) δ 188.3, 176.5, 162.3, 157.9, 145.3, 141.1, 140.3, 134.3, 129.5, 128.6, 128.1, 127.2, 125.7, 123.8, 121.3, 114.6, 107.4, 34.1, 32.5, 21.3 , 12.9; HRMS: 431.1223 [MH] ⁺ Calcd for C ₂₄ H ₁₉ N ₂ O ₆ : 431.1243.

[Example 4] Preparation of anthraquinone compound (4)

Except that 4-(2-(2-methoxyethoxy)ethoxy)aniline (4-(2-(2-Methoxyethoxy)ethoxy)aniline, 3.028 mmol) was used instead of 4-hexylaniline. Reaction was carried out in the same manner as in Example 1 to obtain an anthraquinone compound (4) as a blue solid.

1,8-Dihydroxy-4-((4-(2-(2-methoxyethoxy)ethoxy)phenyl)amino)-5-nitroanthracene-9,10-dione (4): Blue solid; Yield: 69% (0.37 g); mp 94-96 °C; ¹ H NMR (CDCl ₃ , 600 MHz): δ 12.90 (s, 1H), 12.79 (s, 1H), 11.46 (s, 1H), 7.31 (d, J = 9.5 Hz, 1H), 7.09 (d, J = 8.6 Hz, 2H), 7.02-6.96 (m, 2H), 6.92-6.86 (m, 3H), 4.09 (t, J = 4.8 Hz, 2H), 3.81 (t, J = 5.0 Hz, 2H), 3.69 -3.66 (m, 2H), 3.54-3.52 (m, 2H), 3.33 (s, 3H); ¹³ C NMR (CDCl ₃ , 150 MHz) δ 189.2, 184.0, 155.6, 155.3, 144.2, 143.6, 131.7, 129.8, 127.6, 125.1, 125.0, 124.9, 124.7, 114.5, 113.0, 112.8, 110.4, 110.3, 70.9, 69.7 , 68.7, 66.7, 58.0; HRMS: 493.1276 [MH] ⁺ Calcd for C ₂₅ H ₂₁ N ₂ O ₉ : 493.1247.

[Example 5] Preparation of anthraquinone compound (5)

Anthraquinone compound (5) was reacted in the same manner as in Example 1, except that 2-methoxy-5-methylaniline (3.028 mmol) was used instead of 4-hexylaniline. Was obtained as a blue solid.

1,8-dihydroxy-4-((2-methoxy-5-methylphenyl)amino)-5-nitroanthracene-9,10-dione (5): Blue solid; Yield: 85% (0.38 g); mp 190-192 °C; ¹ H NMR (CDCl ₃ , 600 MHz): δ 12.84 (s, 1H), 12.77 (s, 1H), 11.42 (brs, 1H), 7.55 (d, J = 9.0 Hz, 1H), 7.35 (d, J = 9.7 Hz, 1H), 7.21-7.18 (m, 1H), 7.10 (d, J = 9.5 Hz, 1H), 7.00-6.98 (m, 1H), 6.97-6.94 (m, 1H), 6.80 (d, J = 8.2 Hz, 1H), 3.72 (s, 3H), 2.23 (s, 3H); ¹³ C NMR (CDCl ₃ , 150 MHz) δ 189.4, 177.6, 163.3, 159.0, 151.2, 146.0, 130.5, 130.3, 128.9, 128.6, 127.6, 127.0, 126.2, 122.2, 115.7, 112.1, 111.7, 108.6, 55.7, 20.5 ; HRMS: 419.0891 [MH] ⁺ Calcd for C ₂₂ H ₁₅ N ₂ O ₇ : 419.0879.

[Example 6] Preparation of anthraquinone compound (6)

The reaction was carried out in the same manner as in Example 1, except that 4-heptylaniline (3.028 mmol) was used instead of 4-hexylaniline to obtain an anthraquinone compound (6) as a blue solid.

1-((4-heptylphenyl)amino)-4,5-dihydroxy-8-nitroanthracene-9,10-dione (6): Blue solid; Yield: 87% (0.45 g); mp 90-92 °C; ¹ H NMR (CDCl ₃ , 600 MHz) δ 12.84 (s, 1H), 12.75 (s, 1H), 11.66 (s, 1H), 7.54 (d, J = 8.8 Hz, 1H), 7.49 (d, J = 9.5 Hz, 1H), 7.20 (d, J = 8.8 Hz, 1H), 7.15 (d, J = 8.2 Hz, 2H), 7.10 (d, J = 9.7 Hz, 1H), 7.06 (d, J = 8.2 Hz , 2H), 2.55 (t, J = 7.9 Hz, 2H), 1.59-1.52 (m, 2H), 1.31-1.17 (m, 10H), 0.82 (t, J = 7.1 Hz, 3H); ¹³ C NMR (CDCl ₃ , 150 MHz) δ 188.3, 176.5, 162.3, 157.9, 145.3, 141.1, 140.3, 134.3, 129.5, 128.6, 128.1, 127.2, 125.7, 123.8, 121.3, 114.6, 111.1, 107.3, 34.4, 30.7 , 30.3, 28.2, 28.1, 21.6, 13.0; HRMS: 473.1708 [MH] ⁺ Calcd for C ₂₇ H ₂₅ N ₂ O ₆ : 473.1713.

[Example 7] Preparation of anthraquinone compound (7)

Except for using 4-propylaniline (4-Propylaniline, 3.028 mmol) instead of 4-hexylaniline, the reaction was carried out in the same manner as in Example 1 to obtain an anthraquinone compound (7) as a blue solid.

1,8-dihydroxy-4-nitro-5-((4-propylphenyl)amino)anthracene-9,10-dione (7): Blue solid; Yield: 86% (0.39 g); mp 238-240 °C; ¹ H NMR (CDCl ₃ , 600 MHz) δ 12.81 (s, 1H), 12.72 (s, 1H), 11.65 (s, 1H), 7.53 (d, J = 8.8 Hz, 1H), 7.48 (d, J = 9.5 Hz, 1H), 7.19 (d, J = 8.8 Hz, 1H), 7.14 (d, J = 8.0 Hz, 2H), 7.09 (d, J = 9.5 Hz, 1H), 7.05 (d, J = 8.0 Hz , 2H), 2.53 (t, J = 7.7 Hz, 2H), 1.63-1.55 (m, 2H), 0.89 (t, J = 7.3 Hz, 3H); ¹³ C NMR (CDCl ₃ , 150 MHz) δ 189.3, 177.5, 163.3, 158.9, 146.3, 142.1, 141.0, 135.4, 130.5, 129.7, 129.1, 128.2, 126.7, 124.8, 122.3, 115.6, 112.1, 108.4, 37.5, 24.4 , 13.7; HRMS: 417.3960 [MH] ⁺ Calcd for C ₂₃ H ₁₇ N ₂ O ₆ : 417.3981.

[Example 8] Preparation of anthraquinone compound (8)

Preparation of compound a

1,4-dihydroxyanthracene-9,10-dione (1,4-dihydroxyanthracene-9,10-dione, 10 g, 41.66 mmol) was dissolved in acetonitrile (300 mL), and then Et _{3 N (30 mL, 214 mmol} ) and p - toluenesulfonyl chloride was added (p -toluene sulfonyl chloride, 19.2 g , 100 mmol), was stirred under reflux for 5 hours. After completion of the reaction, acetonitrile was removed with a rotary evaporator, and the resulting crude product was dissolved in DCM (Dichloromethane, 500 mL), and then washed with water (2 × 300 mL). The obtained organic layer was dried over anhydrous Na ₂ SO _4, and then the filtrate obtained by filtration was concentrated to obtain a yellow-brown solid. The obtained solid was triturated with diethyl ether and n-hexane to obtain 9,10-dioxo-9,10-dihydroanthracene-1,4-diyl bis(4-methylbenzenesulfonate) (compound a) as a light yellow solid. .

Yield: 8 6% (19.6 g); ¹ H NMR (CDCl ₃ , 600 MHz) δ 8.05 (dd, J = 5.6, 4.3 Hz, 2H), 7.89-7.84 (m, 4H), 7.75 (dd, J = 5.6, 3.3 Hz, 2H), 7.52 ( s, 2H), 7.37-7.31 (m, 4H); ESI-MS: 549 [M+H] ⁺ .

Preparation of compound b-1

Compound a (2 g, 3.646 mmol) was dissolved in DCM (100 mL) at room temperature, then heptylamine (4.375 mmol) was added, followed by stirring for 24 hours. After completion of the reaction, it was concentrated under reduced pressure to obtain a crude compound b-1 as a red solid, which was used in the next step without further purification.

Anthraquinone compounds ( 8) of Produce

Crude compound b-1 (1.0 mmol) was dissolved in pyridine (20 mL) at room temperature, and benzylamine (1.0 mmol) was added, followed by reflux stirring for 16 hours. After completion of the reaction, the crude reaction mixture was directly absorbed into silica gel (230-400 mesh), and then purified by column chromatography (eluent, 4-7% ethyl acetate: n-hexane) to obtain an anthraquinone compound (8) as a blue solid. Obtained as.

1-(benzylamino)-4-(heptylamino)anthracene-9,10-dione (8): Blue solid; Yield: 81% (1.2 g); mp 139-141 °C; ¹ H NMR (600 MHz, CDCl ₃ ) δ 11.06 (s, 1H), 10.66 (s, 1H), 8.31-8.25 (m, 2H), 7.66-7.59 (m, 2H), 7.32-7.18 (m, 5H) ), 7.10-7.05 (m, 2H), 4.61-4.57 (m, 2H), 3.31-3.24 (m, 2H), 1.70-1.63 (m, 2H), 1.16-1.14 (m, 6H), 0.80 (t , J = 7.1 Hz, 3H); ¹³ C NMR (CDCl ₃ , 150 MHz) δ 181.9, 181.3, 145.3, 144.7, 137.6, 133.5, 131.1, 127.8, 126.3, 125.8, 122.7, 122.4, 109.4, 108.7, 45.7, 41.8, 30.7, 28.6, 28.0, 26.1 , 21.5, 13.0; HRMS: 426.2326 [M] ⁺ Calcd for C ₂₈ H ₃₀ N ₂ O ₂ : 426.2307.

[Example 9] Preparation of anthraquinone compound (9)

Preparation of compound b-2

Except for using tridecylamine (4.375 mmol) in place of heptylamine, the reaction was carried out in the same manner as in the preparation method of compound b-1 of Example 8, thereby preparing crude compound b-2 as a red solid. Obtained, which was used in the next step without further purification.

Anthraquinone compounds ( 9) of Produce

The anthraquinone compound (9) was reacted in the same manner as in the preparation method of the anthraquinone compound (8) of Example 8, except that compound b-2 (1.0 mmol) was used instead of compound b-1. Obtained as.

1-(benzylamino)-4-(tridecylamino)anthracene-9,10-dione (9): Blue solid; Yield: 78% (1.5 g); mp 259-261 °C; ¹ H NMR (600 MHz, CDCl ₃ ) δ 8.28-8.25 (m, 2H), 7.67-7.64 (m, 2H), 7.32-7.25 (m, 5H), 7.20-7.18 (m, 1H), 7.15-7.11 (m, 1H), 4.57 (s, 2H), 3.27 (t, J = 7.3 Hz, 2H), 1.75-1.68 (m, 2H), 1.42-1.35 (m, 2H), 1.31-1.15 (m, 18H) ), 0.80 (t, J = 7.1 Hz, 3H); ¹³ C NMR (CDCl ₃ , 150 MHz) δ 183.0, 182.4, 146.4, 145.7, 138.6, 134.6, 134.4, 132.1, 132.0, 128.8, 127.3, 126.9, 123.8, 123.4, 110.5, 109.7, 46.7, 42.9, 31.9, 29.6 , 29.3, 27.1, 22.6, 14.1; HRMS: 510.3257 [M] ⁺ Calcd for C ₃₄ H ₄₂ N ₂ O ₂ : 510.3246.

[Experimental Example] Supercritical dyeing of polyester fiber using an anthraquinone compound as a dye

A polyester fabric (10 g) was suspended on a stainless steel cylinder and then placed in an autoclave reactor. The anthraquinone dye synthesized in Examples 1 to 9 was loaded onto the bottom surface of an autoclave reactor by weighing the amount of dye corresponding to% (o.w.f., On the Weight?Of?Fabric) relative to the weight of the polyether fabric. Different amounts of anthraquinone dye (0.5% (o.w.f.), 1% (o.w.f.) or 1.5% (o.w.f.)) were used for the polyester fabric. The autoclave reactor was sealed, and the autoclave reactor was charged to a freezer below 0°C and cooled for 15 minutes, and then CO2 (100g) was injected into the autoclave reactor from the CO2 line to the set pressure using a valve. At this time, the initial pressure was 5 MPa, and the pressure reached 15 MPa after 10 minutes. After that, a heating bath was installed and gradually heated to a temperature of 120 ℃ for 30 minutes. After performing supercritical fluid dyeing at 120° C. for 1 hour, heating was stopped and gradually cooled, and when it reached 50° C., the heating bath was removed. When the atmospheric pressure was reached, a needle valve was opened to release CO2, and the polyester fiber was taken out from the sample container, washed with soap at 50° C. for 15 minutes, and then washed again with water.

<Evaluation of dyeing characteristics>

In order to find out the factors affecting the dyeing properties of the polyester fiber, an experiment was performed by varying the dye concentration, dyeing temperature, or dyeing pressure.

Change of color strength (K/S) according to dye concentration

Supercritical dyeing experiments were performed over 1 hour at various dye concentrations (0.5%, 1%, or 1.5%) at dyeing pressure (15 MPa) and dyeing temperature (120 °C) to determine the dyeing characteristics due to the dye concentration.

Changes in color intensity (K/S) according to the dye concentration (0.5%, 1%, or 1.5%) from the dyed polyester fiber were observed, and the results are shown in FIG. 1. As shown in Figure 1, the color intensity (K / S) of the dyed polyester fabric is anthraquinone dyes (1), (2), (3), (6), (7) and (9) dyes It increased with increasing concentration, and for the anthraquinone dyes (4) and (5) the color intensity (K/S) reached a maximum at the dye concentration of 1%. That is, in the case of the anthraquinone dye of the present invention, it was found that the color intensity (K/S) also increased as the dye concentration increased.

Change of color intensity (K/S) according to dyeing temperature

To find out the dyeing properties due to dyeing temperature, which plays an important role in the color yield of polyester fibers, various dyeing temperatures of 80 ℃ to 120 ℃ at a constant dye concentration (0.5%) and dyeing pressure (15 MPa). A supercritical dyeing experiment was performed over 1 hour. The results are shown in FIG. 2.

From FIG. 2, it was found that dyeing at a higher temperature can further improve the dye adsorption and diffusion of the polymer chain of the polyester fiber. In particular, dyeing at 120° C. showed the maximum equilibrium capacity of dye adsorption. That is, in the above temperature range, the anthraquinone dye of the present invention not only further increases the solubility in supercritical carbon dioxide, but also increases the diffusion rate of the dye so that the dye dissolved in the supercritical carbon dioxide is easily transferred and adsorbed to the surface and inside of the fiber. And showed excellent color strength (K/S).

Change in color intensity (K/S) according to dyeing pressure

To find out the dyeing characteristics due to the dyeing pressure, which plays a decisive role in the color yield of polyester fibers, at a constant dye concentration (0.5%) and dyeing temperature (120 ℃), various dyeing pressures of 5 to 15 MPa A supercritical staining experiment was performed over 1 hour. The results are shown in FIG. 3.

The density of the supercritical carbon dioxide increased as the pressure increased at the dyeing temperature (120° C.), and the solubility of the anthraquinone dye molecule increased, causing the dye molecule to become amorphous region of the polyester fiber swollen by the supercritical carbon dioxide. Spread quickly. As a result, it was found that the color intensity (K/S) of the dyed polyester fabric was increased (FIG. 3).

4 shows a photograph of a polyester fabric dyed with an anthraquinone dye in supercritical carbon dioxide (supercritical fluid dyeing condition: dye concentration, 0.5%; dyeing pressure, 15 MPa; dyeing temperature, 120° C.; dyeing time, and 1 hours).

<Color intensity (K/S) and dye fixation (%)>

The color intensity (K/S) value of the supercritical dyed polyester fabric (hereinafter referred to as “dyed sample”) was calculated from the reflectance (R%) by the following Kubelka-Munk equation.

The dye fixation rate (F) was calculated by the following equation from (K/S) _dyed (after dyeing) and (K/S) _extracted (after extraction). '(K/S) _extracted ' means the color intensity of the dyed sample from which the dye molecule was extracted by Soxhlet extraction (acetone, 80℃).

(K/S) _dyed and (K/S) _extracted and dye fixation of supercritical carbon dioxide dyed polyester fabric over 1 hour using a dyeing temperature of 120 ℃, a dyeing pressure of 15 MPa and 0.5% anthraquinone dye. The rate (%) was shown in FIG. 5, and it was found that all of them showed excellent fixing rates.

The (K/S) _dyed values of the anthraquinone dyes (1), (6) and (9) were significantly higher compared to other dyes. Anthraquinone dye (4) containing a polyethylene glycol (PEG) chain showed the highest dye fixation rate (93%). This may be because the entropy of mixing is related to the free volume difference between the PEG chain and supercritical carbon dioxide. Anthraquinone dye (1) having a hexyl group (1) is 78%, anthraquinone dye (6) having a heptyl group is 76%, anthraquinone dye (7) having a propyl group is 88%, and an anthraquinone dye (3) having a butyl group is 85%, the anthraquinone dye (2) having a pentyl group showed an excellent fixing rate of 83%.

In addition, the anthraquinone dyes (8) and (9) also showed excellent dye fixation rate (%). In particular, the anthraquinone dyes (8) and (9) in which an amino group is present can further improve the solubility of the dye in supercritical carbon dioxide because carbon dioxide molecules in the supercritical state more advantageously interact with the amino group. This is supported by the density function theory.

<Color characteristic evaluation>

The anthraquinone dye of the present invention has excellent solubility in various common organic solvents such as cyclohexane, hexane, toluene, dichloromethane, acetone and tetrahydrofuran, and is dissolved in an organic solvent to form a dark blue solution.

UV absorption spectra were recorded in acetone solvent (1×10 ^-4 M) in the range of 400-800 nm, anthraquinone compounds (1) to (7) showed a single absorbance maximum, and anthraquinone compound (8) And (9) showed the double absorbance maximum value.

Anthraquinone
compound Absorbance maximum value
(nm) Anthraquinone compounds Absorbance maximum value
(nm) Anthraquinone compounds Absorbance maximum value
(nm) (One) 610 nm (4) 609 nm (7) 614 nm (2) 612 nm (5) 612 nm (8) 595 nm, 640 nm (3) 613 nm (6) 613 nm (9) 594 nm, 642 nm

The reflectance spectra of the dyed polyester fabric was recorded using the white standard BaSO ₄ (white standard BaSO ₄ ).

The maximum value of the reflectance curve is 459 nm for the anthraquinone compound (1), 461 nm for the anthraquinone compound (2), 462 nm for the anthraquinone compound (3), and an anthraquinone compound (4). For 466 nm, for anthraquinone compound (5) 473 nm, for anthraquinone compound (6) 466 nm, for anthraquinone compound (7) 459 nm, for anthraquinone compound (8) 452 nm and anthraquinone In the case of compound (9), 449 nm was centered.

<Color evaluation>

Color evaluation of supercritical dyed polyester fabrics over 1 hour at 0.5% dye concentration, 15 MPa dyeing pressure, and 120° C. dyeing temperature was performed using the CIELAB system to L*, C*, H, a* and b * Values were measured and evaluated, and the results are shown in Table 2 below. L* represents Lightness, C* represents Chroma, and H represents Hue. a* and b* are color perception indexes, the a* value of (-) represents the color change to green, the a* value of (+) represents the color change to red, and the b* value of (-) Represents the color change to blue, and the b* value of (+) represents the color change to yellow.

dyes L* a* b* C* H K/S Anthraquinone compounds (1) 45.90 -12.69 -33.12 35.47 249.09 28.19 Anthraquinone compounds (2) 41.30 -10.46 -32.06 33.73 251.93 8.86 Anthraquinone compounds (3) 46.36 -12.74 -28.51 31.23 245.93 12.66 Anthraquinone compounds (4) 43.29 -13.21 -25.26 28.51 242.39 7.46 Anthraquinone compounds (5) 48.50 -13.67 -21.62 25.58 237.71 7.53 Anthraquinone compounds (6) 41.67 -9.84 -33.05 34.48 253.43 22.30 Anthraquinone compounds (7) 39.41 -10.77 -30.70 32.53 250.67 7.97 Anthraquinone Compound (8) 45.41 -5.76 -38.68 39.11 261.54 15.84 Anthraquinone Compounds (9) 57.91 -8.72 -31.08 32.28 254.33 21.17

From Table 2 above, the color brightness (L*) value of the polyester fabric dyed with supercritical fluid dyeing with the anthraquinone dye of the present invention was 39.41 to 57.91, and among them, the brightness value was 57.91 when using the anthraquinone dye (9) , It was found that the color was brighter than that of using other dyes.

And, it was found that the color hue (H) of the polyester fabric dyed with supercritical fluid with the anthraquinone dye of the present invention was shifted in the green direction on the red-green axis according to the (-) value of the color sensation index a*. . In addition, it can be seen that the color hue (H) of the polyester fabric dyed with supercritical fluid with the anthraquinone dye of the present invention is shifted in the blue direction on the yellow-blue axis according to the value of (-) of the color sensation index b*. there was. That is, the color hue (H) of the anthraquinone dye of the present invention showed good affinity to the polyester fabric at a given temperature.

In addition, according to the color saturation (C*) value, polyester fabrics dyed with supercritical fluid with anthraquinone dye (8) show the brightest color, while polyester with supercritical fluid dyed with anthraquinone dye (5). In the case of the fabric, it was found that it had the darkest color.

In addition, it was found that the K/S value of the polyester fabric dyed with supercritical fluid with the anthraquinone dye of the present invention varied from 7.46 to 28.19.

As described above, it was found that the anthraquinone dye of the present invention has excellent affinity for polyester fabrics during supercritical fluid dyeing, and thus exhibits improved dyeability after supercritical fluid dyeing.

As described above, the present invention has been described by specific matters and limited embodiments, but these are provided only to help a more general understanding of the present invention, and the present invention is not limited to the above embodiments, and the field to which the present invention pertains. Those of ordinary skill in the art can make various modifications and variations from these descriptions.

Therefore, the spirit of the present invention is limited to the described embodiments and should not be defined, and all things that are equivalent or equivalent to the claims as well as the claims to be described later fall within the scope of the spirit of the present invention. .

Claims (8)

Anthraquinone dye for dyeing supercritical fluids represented by the following Formula 1 or 2
[Formula 1]

[Formula 2]

(In Formulas 1 and 2,
R ₁ , R ₂ and R ₃ are each independently hydrogen, C1-C20 alkyl or -(OL) _a -R', provided that R ₁ is C1-C20 alkyl or -(OL) _a -R' ₂ and R ₃ are both hydrogen, and when R ₁ is hydrogen, R ₂ and R ₃ are each independently C1-C20 alkyl or -(OL) _a -R';
L is C1-C20 alkylene; a is an integer from 0 to 10; R'is C1-C20 alkyl or C1-C20 alkoxy;
R ₄ is C1-C20 alkyl; R ₅ is hydrogen, C1-C20 alkyl or C1-C20 alkoxy; m is an integer from 1 to 5.) The method of claim 1,
Anthraquinone dye for dyeing supercritical fluids represented by the following Chemical Formula 3, Chemical Formula 4 or Chemical Formula 5
[Formula 3]

[Formula 4]

[Formula 5]

(In Chemical Formulas 3 to 5,
R ₁ is C1-C20 alkyl or -(OL) _a -R'; L is C1-C20 alkylene; a is an integer from 1 to 10; R'is C1-C20 alkoxy;
R ₂ is C1-C20 alkoxy; R ₃ is C1-C20 alkyl;
R ₄ is C1-C20 alkyl.) The method of claim 2,
R ₁ is C1-C10 alkyl or -(OL) _a -R'; L is C1-C10 alkylene; a is an integer from 1 to 5; R'is C1-C10 alkoxy;
R ₂ is C1-C10 alkoxy; R ₃ is C1-C10 alkyl;
R ₄ is C7-C20 alkyl, an anthraquinone dye for dyeing supercritical fluids. The method of claim 3,
R ₁ is C1-C7 alkyl or -(OL) _a -R'; L is C2-C5 alkylene; a is an integer from 1 to 3; R'is C1-C7 alkoxy;
R ₂ is C1-C7 alkoxy; R ₃ is C1-C7 alkyl, an anthraquinone dye for dyeing supercritical fluids. The method of claim 1,
The anthraquinone dye for supercritical fluid dyeing is any one selected from the following structures, an anthraquinone dye for supercritical fluid dyeing.

A method for dyeing a polyester fiber (PET, polyester fabric) with a supercritical fluid using the anthraquinone dye for dyeing a supercritical fluid according to any one of claims 1 to 5. The method of claim 6,
Wherein the supercritical fluid is supercritical carbon dioxide. The method of claim 6,
When dyeing the supercritical fluid, the dyeing temperature is 80 to 150° C., and the dyeing pressure is 5 to 20 MPa.

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