CN112239604A

CN112239604A - Reactive disperse dye, preparation method and dyeing application thereof

Info

Publication number: CN112239604A
Application number: CN202011324055.XA
Authority: CN
Inventors: 江华; 郭广落
Original assignee: Zhejiang University of Technology ZJUT
Current assignee: Zhejiang University of Technology ZJUT; Zhejiang Sci Tech University ZSTU; Zhejiang University of Science and Technology ZUST
Priority date: 2020-11-24
Filing date: 2020-11-24
Publication date: 2021-01-19
Anticipated expiration: 2040-11-24
Also published as: CN112239604B

Abstract

The invention discloses a reactive disperse dye

The invention also provides a preparation method of the reactive disperse dye, a disperse dye mixture prepared by using the reactive disperse dye, and a disperse dye prepared by using the reactive disperse dyeA dyeing method using the disperse dye mixture. The reactive disperse dye can chemically react with the polyester fiber to form a covalent bond and be firmly combined.

Description

Reactive disperse dye, preparation method and dyeing application thereof

Technical Field

The invention belongs to the fields of fine chemical engineering and textile printing and dyeing, and relates to a reactive disperse dye, a preparation method and a dyeing application thereof.

Background

Polyester fabrics are usually dyed with disperse dyes, and the disperse dyes are mainly combined with polyester fibers by weak acting forces such as van der waals force, hydrogen bonds, hydrophobic effect and the like, so that disperse dye molecules still leave the polyester fibers under severe conditions such as high humidity and heat, and the dyed polyester fabrics have the problems of color fastness reduction and the like.

The existing reactive disperse dye, also called as reactive disperse dye or disperse reactive dye, generally refers to a dye which is produced by introducing reactive groups such as halogenated triazinyl, beta-hydroxyethyl sulfone sulfate and the like into a matrix of the disperse dye, and is specially used for dyeing blended fabrics such as polyester cotton, polyester wool and the like. The dye has the hydrophobicity of disperse dye and the reactivity of active dye, so that the dye can be simultaneously used for coloring synthetic fibers and natural fibers in blended fabrics (refer to Liyunxiang, Qingdao chemical industry, 1989, (1), 21-23).

However, the existing reactive disperse dyes can only react with natural fibers such as cotton and wool due to insufficient reactive capability of active groups, and cannot perform reactive coloring on polyester fibers.

The bis-aziridine compounds are a new class of substances and are widely studied in the fields of materials, chemistry, biology and the like. It is reported (see: Lepage et al, Science 2019,366,875-878) that the bis-aziridine structure forms an active carbene intermediate under high temperature (>100 ℃) or ultraviolet irradiation (wavelength around 350 nm) and thus has the ability to insert oxygen-hydrogen bonds, nitrogen-hydrogen bonds and even carbon-hydrogen bonds. The general structural formula of the bis-aziridines is as follows:

reactive disperse dyes having a bisaziridine structure as a reactive group have not been known.

Disclosure of Invention

The invention aims to provide a reactive disperse dye, a preparation method and a dyeing application thereof.

In order to solve the technical problems, the invention provides a reactive disperse dye, which has the following structural general formula (I):

wherein the content of the first and second substances,

x is-COOCH₂CH₂-、-CH₂OCH₂CH₂-, -CO-or-CH₂-；

R¹Is hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, n-hexyl, cyclohexyl, benzyl or cyanoethyl;

R²、R³respectively hydrogen atom, methyl, ethyl, methoxy, ethoxy, hydroxyl, methylamino, dimethylamino, acetylamino or cyclohexylamino;

R⁴、R⁵、R⁶are respectively selected from hydrogen atom, nitryl, chlorine atom, bromine atom, cyano-group, acetyl or benzoyl.

As an improvement of the reactive disperse dye, the structural formula is any one of the following:

the invention also provides a preparation method of the reactive disperse dye, which is any one of the following methods:

the method comprises the following steps:

adding the raw material A, the raw material C, dicyclohexylcarbodiimide, 4-dimethylaminopyridine and dichloromethane into a container (such as a three-neck flask) under the protection of nitrogen, and stirring for reaction; the reaction temperature is 20-30 ℃, and the reaction time is 12 +/-1 h; the molar ratio of the raw material A to the raw material C to the dicyclohexylcarbodiimide to the 4-dimethylaminopyridine is 1:1:1: 0.1; 1L of dichloromethane is added for every 0.05-1.0 mol of the raw material A; carrying out post-treatment (including silica gel column separation and the like) on the reaction liquid to obtain a reactive disperse dye compound;

the second method,

Adding the raw material C, sodium hydride and tetrahydrofuran into a container (such as a three-neck flask) under the protection of nitrogen, and stirring for reaction; the reaction temperature is 0-5 ℃, and the reaction time is 30 +/-5 min; the molar ratio of the raw material C to the sodium hydride is 1:1, and 1L of tetrahydrofuran is added in every 0.05-1.0 mol of the raw material C; then adding the raw material B, and continuously stirring for reaction; the reaction temperature is 20-30 ℃, and the reaction time is 12 +/-1 h; the molar ratio of the raw material B to the raw material C is 1: 1; carrying out post-treatment (including silica gel column separation and the like) on the reaction liquid to obtain a reactive disperse dye compound;

the structure of the raw material A is as follows:

the structure of the raw material B is as follows:

the structure of the raw material C is as follows:

wherein the content of the first and second substances,

x is a hydrogen atom or HOCH₂CH₂-；

R²、R³is selected from hydrogen atom, methyl, ethyl, methoxy, ethoxy, hydroxyl, methylamino, dimethylamino, acetylamino or cyclohexylamino;

R⁴、R⁵、R⁶is selected from hydrogen atomsNitro, chlorine, bromine, cyano, acetyl or benzoyl.

The invention also provides a disperse dye mixture prepared by using the reactive disperse dye, which comprises the following components in percentage by weight: the disperse dye mixture consists of reactive disperse dye and a dispersing agent according to a mass ratio of 1: 0.5-2;

the dispersant is dispersant NNO, dispersant MF and sodium lignosulfonate.

The invention also provides a preparation method of the disperse dye mixture, which comprises the following steps:

(1) mixing the reactive disperse dye, the dispersing agent and water, and then carrying out high-speed dispersion and sanding (in a sand mill), wherein the sanding speed is 3000 +/-300 revolutions per minute, and the sanding time is 2 +/-0.5 hours, so as to obtain a dispersion liquid; the mass ratio of the water to the reactive disperse dye is 9-11: 1, and the mass ratio of the reactive disperse dye to the dispersing agent is 1: 0.5-2;

(2) and (2) carrying out spray drying on the dispersion liquid obtained in the step (1), wherein the atomization speed is 15-20 ml/min, the inlet temperature is 300 +/-30 ℃, and the outlet temperature is 100 +/-10 ℃, so as to obtain a disperse dye mixture.

The invention also provides a dyeing method carried out by the disperse dye mixture, which comprises the following steps:

(1) in a dye vat, preparing a 0.5-5% owf disperse dye mixture into an aqueous solution, adjusting the pH to 5 (adopting acetic acid), and adding a 5% owf accelerating agent; the accelerating agent is dibutyl succinate;

(2) putting the polyester fabric into a dye vat, sealing the dye vat, and heating to a heat preservation temperature; the heating rate is 2 ℃/min, and the heat preservation temperature is 95 +/-2 ℃; the heat preservation time is 30-60 min (preferably 30 min);

(3) cooling to room temperature, taking out the fabric, washing with clear water, drying in the air, and baking to obtain the dyed polyester fabric; the baking temperature is 120-180 ℃, preferably 140-180 ℃, and more preferably 160 ℃; the baking time is 0.5-2 h, and 2h is more preferable.

In the process of the invention, the inventor imagines that a bisaziridine structure is used in the dye field, and the bisaziridine structure is taken as a reactive group to be combined with a hydrophobic dye parent, so as to create a novel reactive disperse dye, and possibly enable dye molecules to form covalent bond with polyester fibers. However, in practical application, the synthesized bis-aziridine dye has the defects that when the conventional polyester fabric dyeing method is used, only a small amount of dye can be covalently bonded with polyester fibers, and the color fixing rate is low.

The problem with the application of the bis-aziridine structure to the dye field is that: (1) the carbene intermediate is too active to control the reaction with the polyester fiber only; (2) polyester dyeing usually requires high temperatures, and it is concluded from the literature that bis-aziridine must be converted into carbene; (3) complex dyeing mechanism and dyeing process, etc.

Specifically, the polyester fiber, namely polyethylene terephthalate, has no active hydrogen in the structure, only has aliphatic carbon-hydrogen bonds and carbon-hydrogen bonds on a benzene ring, and has lower reaction priority; the dyeing process is that the dye is firstly depolymerized in a water phase into monomolecular dye, then the monomolecular dye is diffused to the surface of the fiber and further enters the fiber, under the condition of high dyeing temperature, the bisaziridine dye inevitably generates carbene in the water phase and preferentially reacts with water molecules to be inactivated, and a large amount of auxiliary agents remained on the surface of the fiber have the possibility of competing reaction.

On the other hand, in order to obtain a wide spectrum of colors, the structure of the dye color body usually contains hydroxyl, amino and other groups, and the groups also participate in the competitive reaction with carbene, which is not favorable for the bonding reaction between the dye and the fiber.

Therefore, the present invention sets a specific dyeing method to solve the above technical problems.

Compared with the prior art, the invention has the following technical effects:

the reactive disperse dye can chemically react with the polyester fiber to form a covalent bond and be firmly combined; the specific dye molecular structure limits the number of oxygen-hydrogen bonds and nitrogen-hydrogen bonds in the dye molecular structure, and can effectively prevent side reactions of the carbene intermediate and the dye; the method of firstly dyeing at low temperature (less than 100 ℃) and then fixing color through high-temperature reaction is adopted during dyeing, and the fact that the diazirine dye can effectively avoid dye inactivation under the dyeing condition of about 95 ℃ for 30min is unexpectedly found, so that the high-reaction color fixing rate is obtained; compared with the conventional disperse dye, the dyed polyester fabric has better color fastness such as soaping resistance, friction resistance, sublimation resistance, solvent extraction resistance and the like; the dye is convenient to synthesize, the dyeing and color fixing operation is simple, the color fixing only needs high-temperature treatment, and the dye has wide application prospect.

Drawings

The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.

FIG. 1 nuclear magnetic resonance hydrogen spectrum of dye (II);

FIG. 2 nuclear magnetic resonance carbon spectrum of dye (II);

FIG. 3 UV-VIS absorption spectrum of dye (II) in N, N-Dimethylformamide (DMF);

FIG. 4K/S curve of dye (II) dyed polyester fabric;

FIG. 5 nuclear magnetic resonance hydrogen spectrum of dye (III);

FIG. 6 nuclear magnetic resonance carbon spectrum of dye (III);

FIG. 7 UV-VIS absorption spectrum of dye (III) in N, N-Dimethylformamide (DMF);

FIG. 8 is a K/S curve of dye (III) dyeing a polyester fabric;

FIG. 9 is a reaction mechanism diagram of the reactive disperse dye and the polyester fiber.

Detailed Description

The present invention will be described in detail and specifically by the following examples to better understand the present invention, but the following examples do not limit the scope of the present invention. Compounds 1, 5 and 12 are commercially available or can be synthesized according to methods provided in the literature (J.fluorine chem.2012,140, 62-69; Angew.chem.int.Ed.2018,57, 16688-; compounds 2-4, 6-11 are commercially available.

Example 1: synthesis of dye (II)

Under the protection of nitrogen and at room temperature, sequentially adding compound 1(2mmol, 0.460g), compound 2(2mmol, 0.534g), dicyclohexylcarbodiimide (2mmol, 0.413g), 4-dimethylaminopyridine (0.2mmol, 0.025g) and dichloromethane (20ml) into a three-neck flask, stirring and reacting at 20-30 ℃ for 12h, monitoring the reaction by adopting thin layer chromatography, and stopping the reaction after the raw materials are consumed after 12 h.

40ml of water and 20ml of dichloromethane were added, extraction was carried out three times (dichloromethane 40 ml. times.3), the organic phases were combined, the solvent (dichloromethane) was distilled off using a rotary evaporator, and the residue was separated by 200 to 300 mesh silica gel column chromatography (eluent: petroleum ether/ethyl acetate. RTM. 5/1, V/V) to give dye (II) as a yellow solid, 0.80g, yield 83.1%.

¹H NMR(CDCl₃,400MHz)δ8.03(d,J＝7.6Hz,2H),7.88(d,J＝7.6Hz,2H),7.85(d,J＝7.6Hz,2H),7.48(dd,J¹＝J²＝7.6Hz,2H),7.39(dd,J¹＝7.2Hz,J²＝7.6Hz,1H),7.24(d,J＝7.6Hz,2H),6.84(d,J＝7.6Hz,2H),4.54(t,J¹＝6.4Hz,J²＝6.0Hz,2H),3.80(t,J¹＝6.4Hz,J²＝6.0Hz,2H),3.55(q,J＝7.2Hz,2H),1.26(t,J＝7.2Hz,3H).¹³C NMR(CDCl₃,100MHz)δ165.52,153.19,150.02,143.90,134.06,130.87,129.98,129.52,128.96,126.45,125.22,122.25,121.86(q,J＝273Hz),111.52,62.53,48.82,45.60,29.72,12.36.ESI-MS:m/z＝482.2[M+H].

Example 2: synthesis of dye (III)

Replacement of Compound 2 with Compound 3(2mmol, 0.697g), the remainder being identical to example 1, gave dye (III) as a red solid, 0.98g, yield 87.4%.

¹H NMR(CDCl₃,400MHz)δ8.40(d,J＝2.4Hz,1H),8.16(dd,J¹＝8.4Hz,J²＝2.4Hz,1H),8.04(d,J＝7.6Hz,2H),7.95(d,J＝7.6Hz,2H),7.78(d,J＝7.6Hz,1H),7.24(d,J＝7.6Hz,2H),6.86(d,J＝7.6Hz,2H),4.56(t,J＝6.4Hz,2H),3.84(t,J＝6.4Hz,2H),3.59(q,J＝7.2Hz,2H),1.28(t,J＝7.2Hz,3H).¹³C NMR(CDCl₃,100MHz)δ165.46,153.04,151.66,147.27,144.55,134.17,134.07,130.68,129.97,126.94,126.47,126.02,122.61,121.83(q,J＝273Hz),118.04,111.63,62.24,48.84,45.83,28.61,12.37.ESI-MS:m/z＝561.1[M+H].

Example 3: synthesis of dye (IV)

Replacement of Compound 2 with Compound 4(2mmol, 1.118g), the remainder being identical to example 1, gave dye (IV) as a blue solid, 1.05g, yield 68.1%.

¹H NMR(CDCl₃,400MHz)δ8.47(dd,J¹＝6.4Hz,J²＝2.0Hz,2H),7.74(d,J＝7.6Hz,2H),7.52(m,4H),6.81(d,J＝7.6Hz,2H),4.48(t,J＝4.4Hz,2H),4.06(t,J＝4.4Hz,2H),3.29(q,J＝8.0Hz,2H),1.10(t,J＝8.0Hz,3H).ESI-MS:m/z＝771.0[M+H].

Example 4: synthesis of dye (V)

Adding compound 2(2mmol, 0.534g), sodium hydride (60% wt in mineral oil, 2mmol, 0.080g) and tetrahydrofuran (20ml) into a three-neck flask under the protection of nitrogen and at 0 ℃, and stirring for reaction for 30 min; compound 5(2mmol, 0.558g) was added to the reaction solution and stirred at room temperature for further reaction for 12 h; the reaction was monitored by thin layer chromatography and stopped after 12h of complete consumption of starting material.

40ml of water and 20ml of ethyl acetate were added, extraction was carried out three times (ethyl acetate 40 ml. times.3), the organic phases were combined, the solvent was distilled off using a rotary evaporator, and the residue was separated by silica gel column chromatography (eluent: petroleum ether/ethyl acetate. times. 5/1) to give dye (V) as a yellow solid, 0.83g, yield 88.7%.

¹H NMR(CDCl₃,400MHz)δ7.82(d,J＝7.6Hz,2H),7.77(dd,J¹＝7.6Hz,J²＝2.0Hz,2H),7.54(dd,J¹＝7.6Hz,J²＝7.2Hz,2H),7.47-7.44(m,3H),7.39(d,J＝7.6Hz,2H),6.69(d,J＝7.6Hz,2H),4.47(s,2H),3.77(t,J＝4.4Hz,2H),3.71(t,J＝4.4Hz,2H),3.29(q,J＝8.0Hz,2H),1.10(t,J＝8.0Hz,3H).ESI-MS:m/z＝468.2[M+H].

Example 5: synthesis of dye (VI)

Compound 2 was replaced with Compound 6(2mmol, 0.629g), the remainder was identical to example 4 to give dye (VI), a red solid, 0.84g, yield 82.0%,

¹H NMR(CDCl₃,400MHz)δ8.30(d,J＝7.6Hz,2H),7.86-7.83(m,4H),7.45(m,4H),6.80(d,J＝7.6Hz,2H),4.47(s,2H),3.79-3.76(m,2H),3.73-3.69(m,2H),3.29(q,J＝8.0Hz,2H),1.10(t,J＝8.0Hz,3H).ESI-MS:m/z＝512.2[M+H].

example 6: synthesis of dye (VII)

Replacement of Compound 2 by Compound 7(2mmol, 0.842g), the remainder being identical to example 4, gave dye (VII) as a blue solid, 0.93g, yield 75.0%.

¹H NMR(CDCl₃,400MHz)δ9.50(s,1H),8.92-8.91(m,2H),8.27(d,J＝1.6Hz,1H),7.44-7.39(m,5H),6.96(d,J＝7.2Hz,1H),4.47(s,2H),3.79-3.75(m,2H),3.73-3.69(m,2H),3.29(q,J＝8.0Hz,2H),2.16(s,3H),1.10(t,J＝8.0Hz,3H).ESI-MS:m/z＝620.2[M+H].

Example 7: synthesis of dye (VIII)

Replacement of Compound 2 with Compound 8(2mmol, 0.394g), the remainder being identical to example 1, gave dye (VIII) as a yellow solid, 0.71g, yield 86.7%.

¹H NMR(CDCl₃,400MHz)δ7.89(s,1H),7.76(d,J＝7.6Hz,2H),7.73-7.70(m,4H),7.55-7.51(m,4H),7.47-7.42(m,1H),7.26(d,J＝7.6Hz,2H).ESI-MS:m/z＝410.1[M+H].

Example 8: synthesis of dye (IX)

Compound 2 was replaced with Compound 9(2mmol, 0.642g), and the remainder was identical to example 1 to give dye (IX), a red solid, 0.89g, yield 83.4%,

¹H NMR(CDCl₃,400MHz)δ8.50(d,J＝1.6Hz,1H),8.26(dd,J¹＝7.2Hz,J²＝2.0Hz,1H),7.89(s,1H),7.87(d,J＝7.6Hz,1H),7.81(d,J＝7.6Hz,2H),7.71(d,J＝7.2Hz,2H),7.54(d,J＝7.6Hz,2H),7.27(d,J＝7.2Hz,2H).ESI-MS:m/z＝533.0[M+H].

example 9: synthesis of dye (X)

Compound 2 was replaced with Compound 10(2mmol, 0.790g), and the remainder was identical to example 1 to give dye (X), a blue solid, 0.95g, yield 78.2%,

¹H NMR(CDCl₃,400MHz)δ8.84(d,J＝2.0Hz,1H),8.81(d,J＝2.0Hz,1H),8.70(s,1H),7.73(d,J＝7.2Hz,2H),7.55(d,J＝7.6Hz,2H),7.15(d,J＝1.6Hz,1H),7.07-7.00(m,2H),3.75(s,1H),2.82(s,3H).ESI-MS:m/z＝607.0[M+H].

example 10: synthesis of dye (XI)

Replacement of compound 2 with compound 8(2mmol, 0.394g), otherwise identical to example 4, gave dye (XI) as a yellow solid, 0.70g, 88.5% yield.

¹H NMR(CDCl₃,400MHz)δ7.73(dd,J¹＝7.6Hz,J²＝2.0Hz,2H),7.58-7.51(m,4H),7.47-7.42(m,3H),7.38(d,J＝7.6Hz,2H),6.75(d,J＝7.2Hz,2H),4.64(s,1H),4.32(s,2H).ESI-MS:m/z＝396.1[M+H].

Example 11: synthesis of dye (XII)

Replacement of Compound 2 with Compound 9(2mmol, 0.642g), the remainder being identical to example 4, gave dye (XII) as a red solid, 0.87g, 83.8% yield.

¹H NMR(CDCl₃,400MHz)δ8.50(d,J＝2.4Hz,1H),8.26(dd,J¹＝7.6Hz,J²＝2.4Hz,1H),7.90(d,J＝7.6Hz,1H),7.63(d,J＝7.6Hz,2H),7.45-7.37(m,4H),6.77(d,J＝7.6Hz,2H),4.56(s,1H),4.32(s,2H).ESI-MS:m/z＝519.0[M+H].

Example 12: synthesis of dye (XIII)

Compound 2 was replaced with compound 11(2mmol, 0.806g), and the remainder was identical to example 4 to give dye (XIII), a blue solid, 0.95g, yield 78.0%.

¹H NMR(CDCl₃,400MHz)δ9.50(s,1H),8.79(d,J＝2.0Hz,1H),8.64(d,J＝2.0Hz,1H),8.78(d,J＝7.2Hz,1H),7.44(d,J＝7.6Hz,2H),7.39(d,J＝7.6Hz,2H),6.71(d,J＝2.0Hz,1H),6.64(dd,J¹＝7.6Hz,J²＝2.0Hz,1H),4.77(s,1H),4.32(s,2H),2.05(s,3H).ESI-MS:m/z＝601.0[M+H].

Comparative example 1: synthesis of contrast dye M

Compound 12(2mmol, 0.436g) was substituted for Compound 1 in example 1 and the remainder was identical to example 1 to give comparative dye M as a yellow solid in a yield of 80.8%,¹H NMR(CDCl₃,400MHz)δ8.01(d,J＝7.6Hz,2H),7.73(dd,J¹＝7.6Hz,J²＝2.0Hz,2H),7.58-7.51(m,4H),7.47-7.42(m,3H),6.75(d,J＝7.6Hz,2H),4.65(s,1H),4.32(s,2H).ESI-MS:m/z＝384.1[M+H].

comparative example 2 Synthesis of comparative dye N

A comparative dye N was obtained by substituting compound 13(2mmol, 0.776g) for compound 2 in example 1 and making the same as in example 1.

Compound 13 can be referred to: bioconjugate Chemistry,2006, 17(3), 670-.

Examples of dye mixtures: preparation of dye mixtures

2.0g of dye (II), 2.0g of dispersant NNO and 20g of water are added into a sand mill to be mixed, then high-speed dispersion and sand milling are carried out, the sand milling speed is 3000 r/min, the sand milling time is 2 hours, after the sand milling is finished, the obtained dispersion liquid is spray dried (the atomization speed is 15ml/min, the inlet temperature is 300 ℃, the outlet temperature is 100 ℃) to obtain the dye mixture, and the number 1 is obtained.

The dyes obtained in the preceding examples and commercially available commercial dyes were prepared in this way, the numbers of the dye mixtures obtained with the dyes (III) to (XIII) being 2 to 12, respectively, the number 13 for the dye mixture obtained with the comparison dye M, the number 14 for the dye mixture obtained with the comparison dye N, and the number 15 for the dye mixture obtained with the commercially available commercial dye C.I. disperse yellow 23; the dye mixture obtained using the commercially available commercial dye reactive disperse yellow GR corresponds to code 16.

C.i. disperse yellow 23 has the structure:

the structure of the active disperse yellow GR is as follows:

experiment one: dissolving 0.040g of the dye mixture with the number 1 in 100ml of deionized water to prepare an aqueous solution, placing the aqueous solution in a dye vat, adjusting the pH value of the aqueous solution to 5 by adopting acetic acid, and adding 0.1g of dibutyl succinate serving as an accelerating agent; placing 2g of polyester fabric, sealing the dye vat, heating to 95 ℃ at the speed of 2 ℃/min, and keeping the temperature for 30 min; after dyeing is finished, naturally cooling the dye vat to room temperature, taking out the fabric, washing the fabric with clear water, airing the fabric, and putting the fabric into a baking oven at 160 ℃ for baking for 2 hours to obtain a dyed polyester fabric; and testing the surface Color depth value (K/S) of the dyed fabric by using a Data Color measuring and matching instrument.

Description of the drawings: the purpose of adding the accelerating agent is to ensure that the dye can well enter the interior of the polyester fiber at a lower temperature; the further purpose is to reduce the temperature during dyeing and ensure that the bis-aziridine in the dye structure can be stably present in a complex dyeing environment; after dyeing, the auxiliary agent is washed off the fiber and dried (moisture is removed), so that only dye and polyester fiber are used in baking, and the color fixing rate is ensured.

Experiment two: and (3) putting the dyed polyester fabric obtained in the first experiment into a single-neck flask filled with N, N-dimethylformamide (100ml), heating to 120 ℃, keeping for 30min, taking out the fabric, cooling, washing with clear water, airing, and testing the K/S value of the fabric. The dye mixtures with the numbers 2-16 are tested according to the first test method and the second test method, and the results are shown in the table 1:

TABLE 1

The color fixing rate calculation method comprises the following steps: the fixation rate (K/S value of dyed fabric after extraction with experiment two solvents)/(K/S value of dyed fabric for experiment one).

The results in table 1 show that the polyester fabrics dyed by the dyes (II) to (XIII) have good color yield, most of the dyes remain on the fiber after the extraction with N, N-dimethylformamide, and the color fixing rate is above 60%, and it can also be seen that the color fixing rate decreases from about 80% to less than 65% as the number of N-H bonds in the molecular structure of the dyes increases. The result of the number 13 shows that after the structure of the diazirine is removed from the dye molecule, the dye on the dyed fabric is completely extracted by the N, N-dimethylformamide without reaction capability; the result of the number 14 shows that when the molecular structure of the dye contains a plurality of hydroxyl groups, the fixation rate is also obviously reduced, and the suspected reason is that the carbene intermediate reacts with the hydroxyl groups on the self structure of the dye and cannot be combined with the fiber; the result of the number 15 shows that no covalent bond exists between the commercial disperse dye C.I. disperse yellow 23 and the polyester fiber, and the dye on the fiber can be completely extracted by N, N-dimethylformamide; the result of the number 16 shows that a covalent bond cannot be formed between the commercially available reactive disperse dye containing the chlorotriazine reactive group and the polyester fiber; the results indirectly prove that the dye provided by the invention can be effectively combined with the polyester fiber through covalent bonds.

Experiment three: the soaping fastness, the rubbing fastness and the sublimation fastness of each dyed fabric in the first test experiment are tested according to the standards GB/T3921-2008, GB/T3920-2008 and GB/T6152-1997. The results are shown in Table 2.

TABLE 2

From the results in table 2, it can be seen that the reactive disperse dye dyed fabric provided by the present invention has good fastness to soaping, rubbing and sublimation.

Comparing experiment 1, and adopting the dye mixture of number 1 to carry out experiment one and experiment two, changing the heat preservation temperature in experiment one to 70 ℃, and the rest are equal.

Comparing experiment 2, and adopting the dye mixture with the number 1 to carry out experiment one and experiment two, the heat preservation temperature in experiment one is changed to 120 ℃, and the rest are equal.

Comparing experiment 3, and carrying out experiment I and experiment II by adopting the dye mixture with the number 1, wherein the heat preservation time in experiment I is changed into 10min, and the rest are equal.

Comparing experiment 4, carrying out experiment I and experiment II by adopting the dye mixture with the number 1, wherein the heat preservation time in experiment I is changed to 60min, and the rest are equal.

Comparing experiment 5, and adopting the dye mixture of number 1 to carry out experiment one and experiment two, changing the baking temperature in experiment one to 120 ℃, and the rest are equal.

Comparing experiment 6, and adopting the dye mixture of number 1 to carry out experiment one and experiment two, changing the baking temperature in experiment one to 140 ℃, and the rest are equal.

Comparing experiment 7, and adopting the dye mixture of number 1 to carry out experiment one and experiment two, changing the baking temperature in experiment one to 180 ℃, and the rest are equal.

Comparing experiment 8, and performing experiment I and experiment II by using the dye mixture of number 1, wherein the baking time in experiment I is changed to 0.5h, and the rest are equal.

Comparative experiment 9, experiment one and experiment two were carried out using the dye mixture of No. 1, where experiment one was not baked after dyeing was completed and the others were identical.

Comparative experiment 10, dyeing with the dye mixture No. 1 and using the currently most popular conventional high temperature high pressure dyeing method for dacron. Dissolving 0.040g of the dye mixture with the number 1 in 100ml of deionized water to prepare an aqueous solution, placing the aqueous solution in a dye vat, and adjusting the pH value of the aqueous solution to 5 by adopting acetic acid; placing 2g of polyester fabric, sealing the dye vat, heating to 130 ℃ at the speed of 2 ℃/min, and keeping the temperature for 60 min; after dyeing is finished, naturally cooling the dye vat, taking out the fabric, and washing the fabric with clear water to obtain a dyed polyester fabric; and testing the surface Color depth value (K/S) of the dyed fabric by using a Data Color measuring and matching instrument. And a second experiment was performed.

A comparison experiment 11, namely baking the dyed polyester fabric (fabric before the experiment II) obtained by adopting the high-temperature high-pressure dyeing method in the comparison experiment 10 in a baking oven at 160 ℃ for 2 hours; and then testing the surface Color depth value (K/S) of the dyed fabric by using a Data Color measuring and matching instrument. And a second experiment was performed.

The dyed fabrics from comparative experiment 1 to comparative experiment 11 and the dyed fabrics after extraction were tested for K/S values and the results are shown in table 3:

TABLE 3

As can be seen from the results in Table 3, the comparative experiment 1 shows that when the heat preservation temperature is insufficient during dyeing, the dye is less dyed on the polyester fiber, so that the dyeing is not deep; a comparative experiment 2 shows that the color fixing rate is reduced on the contrary when the temperature is too high during dyeing, and the guessed reason is probably that the generated carbene intermediate reacts with water to be inactivated due to too high temperature; a comparison experiment 3 shows that when the heat preservation time is short, the color depth value of the polyester fiber dyed by the dye is not high; a contrast experiment 4 shows that the color fixing rate is reduced to some extent due to overlong heat preservation time; comparative experiments 5 and 6 show that when the baking temperature is insufficient, the color fixing rate is low; a comparison experiment 8 shows that when the baking time is insufficient, the color fixing rate is low; comparative experiment 9 shows that the dye cannot be bonded with the fiber by covalent bonds without baking treatment; a comparative experiment 10 shows that the bisaziridine dye is difficult to combine with the polyester fiber when the disperse dye is used for dyeing by a conventional high-temperature high-pressure method, and the suspected reason is that the carbene intermediate is inactivated by reacting with water due to high temperature; comparative experiment 11 shows that the polyester fabric dyed by the high-temperature and high-pressure dyeing method cannot be recombined with the fiber even if the polyester fabric is baked, and further shows that the bisaziridine dye is inactivated.

Finally, it is also noted that the above-mentioned lists merely illustrate a few specific embodiments of the invention. It is obvious that the invention is not limited to the above embodiments, but that many variations are possible. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.

Claims

1. A reactive disperse dye is characterized by having the following structural general formula (I):

wherein the content of the first and second substances,

x is-COOCH₂CH₂-、-CH₂OCH₂CH₂-, -CO-or-CH₂-；

R²、R³respectively is a hydrogen atom, a methyl group, an ethyl group, a methoxy group,Ethoxy, hydroxy, methylamino, dimethylamino, acetylamino or cyclohexylamino;

2. The reactive disperse dye according to claim 1, wherein the structural formula is any one of:

3. a process for the preparation of a reactive disperse dye according to claim 1 or 2, characterized by being any one of the following processes:

the method comprises the following steps:

under the protection of nitrogen, adding the raw material A, the raw material C, dicyclohexylcarbodiimide, 4-dimethylaminopyridine and dichloromethane into a container, and stirring for reaction; the reaction temperature is 20-30 ℃, and the reaction time is 12 +/-1 h; the molar ratio of the raw material A to the raw material C to the dicyclohexylcarbodiimide to the 4-dimethylaminopyridine is 1:1:1: 0.1; post-treating the reaction solution to obtain a reactive disperse dye compound;

the second method,

Under the protection of nitrogen, adding the raw materials C, sodium hydride and tetrahydrofuran into a container, and stirring for reaction; the reaction temperature is 0-5 ℃, and the reaction time is 30 +/-5 min; the molar ratio of the raw material C to the sodium hydride is 1: 1; then adding the raw material B, and continuously stirring for reaction; the reaction temperature is 20-30 ℃, and the reaction time is 12 +/-1 h; the molar ratio of the raw material B to the raw material C is 1: 1; post-treating the reaction solution to obtain a reactive disperse dye compound;

the structure of the raw material A is as follows:

the structure of the raw material B is as follows:

the structure of the raw material C is as follows:

wherein the content of the first and second substances,

x is a hydrogen atom or HOCH₂CH₂-；

R⁴、R⁵、R⁶is selected from hydrogen atom, nitro, chlorine atom, bromine atom, cyano, acetyl or benzoyl.

4. A disperse dye mixture prepared using the reactive disperse dye of claim 1 or 2, wherein: the disperse dye mixture consists of reactive disperse dye and a dispersing agent according to a mass ratio of 1: 0.5-2;

the dispersant is dispersant NNO, dispersant MF and sodium lignosulfonate.

5. A process for the preparation of a disperse dye mixture according to claim 4, comprising the steps of:

(1) mixing the reactive disperse dye, the dispersing agent and water, and then carrying out high-speed dispersion and sanding, wherein the sanding speed is 3000 +/-300 revolutions per minute, and the sanding time is 2 +/-0.5 hours, so as to obtain a dispersion liquid; the mass ratio of the water to the reactive disperse dye is 9-11: 1, and the mass ratio of the reactive disperse dye to the dispersing agent is 1: 0.5-2;

6. Dyeing process carried out with a mixture of disperse dyes according to claim 4, characterized in that it comprises the following steps:

(1) preparing a 0.5-5% owf disperse dye mixture into an aqueous solution, adjusting the pH to 5, and adding a 5% owf accelerating agent; the accelerating agent is dibutyl succinate;

(2) placing the terylene fabric, sealing the dye vat, and heating to a heat preservation temperature; the heating rate is 2 ℃/min, and the heat preservation temperature is 95 +/-2 ℃; the heat preservation time is 30-60 min;

(3) cooling, taking out the fabric, washing with clear water, drying in the air, and baking to obtain the dyed polyester fabric; the baking temperature is 120-180 ℃; the baking time is 0.5-2 h.