CN104693141A - Disperse dye compound as well as preparation method and use of disperse dye compound - Google Patents

Abstract

The invention discloses a disperse dye compound and its preparation method and application. Its structural formula is shown in formula 1:Formula 1; the present invention selects CI disperse blue 106 dye, carries out coupling reaction with diformyl chloride compound, prepares described disperse dye compound, when this disperse dye compound is applied to spandex or polylactic acid fiber dyeing, washing fastness, sublimation fastness With obvious improvement.

Description

A kind of disperse dye compound and its preparation method and application

Technical field:

The invention relates to a novel disperse dye, in particular to a disperse dye compound and its preparation method and application.

Background technique:

Disperse dyes were first used in acetate fibers, and then developed rapidly with the development of polyester fibers (polyester). Now there are many kinds of disperse dyes and complete chromatograms. According to the structure, they can be divided into azo type, anthraquinone type, methine type, o-nitroaniline type and so on. Among them, the most interesting chemical structures are azo and anthraquinone type disperse dyes. Disperse dyes with azo structure have the advantages of relatively complete chromatogram, high color intensity (that is, high molar extinction coefficient), easy manufacture and good economy. Anthraquinone-type disperse dyes have the characteristics of vividness, high light fastness and excellent dyeing performance, but there are also obvious disadvantages, such as low color intensity and high price. In recent years, heterocyclic disperse dyes have become a research topic in the dye industry due to their bright shade, high color strength, good fastness, good dark color effect, high molar extinction coefficient, and good dyeing performance. A larger area. In addition, in the process of developing and screening dyes for polyester microfibers, it was also found that heterocyclic disperse dyes have better application performance than other types of disperse dyes, which has attracted extensive attention of researchers. The heterocyclic dyes synthesized in recent years are mainly through the introduction of nitrogen, sulfur, oxygen and other heteroatoms into the diazo component or coupling component of the dye. Most of them are bright in color, strong in applicability, and have broad development prospects.

Disperse dyes are a kind of non-ionic dyes with very low water solubility and mainly exist in dispersed state in the form of fine particles in water during dyeing. According to the principle of similar compatibility, it is mainly used for dyeing hydrophobic fibers such as polyester, polyamide and acetate. However, due to the different fiber structures, the dyeing performance of the same dye on different fibers is also quite different. At present, according to the dyeing performance and process requirements of different fibers, people in the industry screen disperse dyes to obtain a special series of disperse dyes suitable for a certain fiber or a certain process, and label them with corresponding product names to meet market demand.

With the emergence of new fibers such as polyurethane fibers, polylactic acid fibers, and easily dyeable modified polyester (ECDP for short), it is difficult for existing disperse dyes to meet their dyeing performance requirements, and low tinting strength and poor color fastness generally occur. It is difficult to fundamentally solve the problem by only relying on screening and dyeing process improvement. Tracing it to its cause, be because the glass transition temperature of these fibers is relatively low, the space that the sub-segment movement of the amorphous region produces is more larger, and the phenomenon that disperse dyes appear easy to enter and come out when dyeing, shows that existing disperse dyes The affinity of this type of fiber is not large enough, which leads to thermal migration from the inside to the outside due to the intensification of the thermal movement of the dye molecules when the fiber is heated. Therefore, improving the thermal migration resistance of disperse dyes has become a research hotspot in the industry.

Invention content:

The purpose of the first aspect of the present invention is to provide a novel disperse dye compound, which has a remarkable effect on the dyeing of spandex and polylactic acid fibers.

The technical scheme that the present invention takes is as follows:

A kind of disperse dye compound, its structural formula is as shown in formula 1:

Formula 1.

The above-mentioned disperse dye compound of the present invention contains two azo disperse dye precursors and two ester groups (-COO-), and the characteristics of this structure are:

(1) Effectively increase the molecular volume and molecular weight of the dye, thereby increasing the contact surface and van der Waals force between the dye and the fiber, and improving the affinity of the dye to the fiber.

The dyeing mechanism of disperse dyes shows that disperse dyes are combined with fibers by van der Waals force, hydrogen bond and charge transfer intermolecular force. The van der Waals force between dyes and fibers depends on the structure and shape of molecules, and is related to the contact area between them and the distance between molecules. Generally, the greater the relative molecular weight of the dye, the more complex the structure, the longer the conjugated system, the better the linearity and co-planarity, and it is suitable for the molecular structure of the fiber, and the van der Waals force is generally larger.

(2) By introducing the characteristic group of ester group (-COO-), it can form a hydrogen bond with the hydrogen-donating group in the fiber, and is suitable for the structure of the polyester fiber.

(3) The structural formula of the new disperse dye contains two independent chromophores, which will not change the shade too much.

The second aspect object of the present invention is to provide a kind of preparation method of aforementioned disperse dye compound, it is characterized in that, comprise the following steps: select C.I. .

further:

Add 1.00g of purified and vacuum-dried C.I. Disperse Blue 106 dye to a 500ml three-necked flask, add an appropriate amount of dehydrated 300ml of dichloromethane as a solvent, stir to completely dissolve the disperse dye, add 0.61g for dehydration Accurately weigh 0.40g of diformyl chloride compound, dissolve and dilute it with an appropriate amount of reaction solvent, slowly drop it into the stirred reactor in an ice bath, and react at room temperature for 2-4h; thin-layer sample tracking reaction Process, after the reaction is completed, add 100ml of dilute acid-containing aqueous solution, extract and separate, spin the dye solution to remove the dichloromethane solvent, then wash and filter with an appropriate amount of sodium carbonate solution, and wash with water to obtain 1.18g of the crude product.

The crude product of the prepared disperse dye compound is recrystallized from dimethylformamide to obtain the pure product of the disperse dye compound.

The purpose of the third aspect of the present invention is to provide a kind of purposes of above-mentioned disperse dye compound in spandex or polylactic acid fiber dyeing, confirm through experiment, adopt above-mentioned disperse dye compound, spandex, polylactic acid fiber are dyed, and 1:1 Standard dyed samples were tested for color fastness. The test results showed that the washing fastness of spandex and polylactic acid fiber dyed samples were significantly improved, and the dry heat fastness of spandex color samples was also significantly improved.

Below in conjunction with accompanying drawing and specific embodiment, the present invention is described in further detail:

Description of drawings:

Fig. 1 is the mass spectrogram of the disperse dye compound that the embodiment of the present invention prepares;

Fig. 2 is the nuclear magnetic resonance figure of the disperse dye compound that the embodiment of the present invention prepares;

Fig. 3 is the infrared spectrum analysis contrast figure of the disperse dye compound prepared by the embodiment of the present invention and C.I. disperse blue 106;

Fig. 4 is a graph comparing the absorption spectrum curves of the disperse dye compound prepared in the embodiment of the present invention and C.I. disperse blue 106.

Detailed ways:

Example 1:

Add 1.00g of purified and vacuum-dried C.I. Disperse Blue 106 dye to a 500ml three-necked flask, add an appropriate amount of dehydrated 300ml of dichloromethane as a solvent, stir to completely dissolve the disperse dye, add 0.61g for dehydration Accurately weigh 0.40g of diformyl chloride compound, dissolve and dilute it with an appropriate amount of reaction solvent, slowly drop it into a stirred reactor in an ice bath, and raise the temperature to room temperature for 2-4h. TLC spotting to trace the reaction process, after the reaction is completed, add 100ml of aqueous solution containing dilute acid, extract and separate, spin the dye solution to remove the dichloromethane solvent, then wash and filter with an appropriate amount of sodium carbonate solution, and wash with water to obtain 1.18g of crude product , and the yield was 84.29%.

The crude product is recrystallized from dimethylformamide to obtain the pure product of the novel disperse dye compound (hereinafter referred to as the new dye).

Product Confirmation:

(1) Molecular structural formula:

(3) Molecular structure characterization:

Mass Spectrometry: MS(+ESI): m/z(%)=801(100)[M+H] ⁺ .

NMR analysis: 1H NMR (400MHz, CDCl3) ppm 8.60(s, 2H), 8.04(s, 4H), 8.00(d, J＝9.2Hz, 2H), 6.72(dd, J＝9.2, 2.8Hz, 2H) ,6.69(s,2H),4.59(t,J=6.0Hz,4H),3.89(t,J=6.0Hz,4H),3.65(q,J=6.8Hz,4H),2.62(s,6H) , 1.32 (t, J=6.8Hz, 6H).

Infrared spectrum analysis: as shown in Figure 3.

From the comparison in the figure, it is found that in the infrared spectrum of the new dye, there is no hydroxyl stretching vibration peak ν _OH in the range of 3200-3500cm ^-1 , and a new characteristic peak ν _C of the ester group (-COO-) at 1718cm ^-1 is added. _=O , while the other peaks remained basically unchanged, indicating that the hydroxyl group in CI disperse blue 106 reacted with terephthaloyl chloride to generate a new coupled disperse dye.

(4) Spectral absorption performance:

Weigh 0.01 gram of new dye, dissolve it in 100ml N,N-dimethylformamide, dilute it 10 times to make the concentration 0.01g/L, and measure the absorption by UV-2450 ultraviolet-visible spectrophotometer (Shimadzu Corporation, Japan). Spectral curve, and compared with the absorption spectrum curve of 0.01g/L C.I. disperse blue 106 solution of the same concentration of the original dye, see Figure 4.

From the absorption spectrum curve in the figure, it can be found that compared with the original dye C.I. Disperse Blue 106, the maximum absorption wavelength of the new dye 3 has shifted to the short wavelength direction by 14nm, from the original 613nm to 599nm, and the molar extinction coefficient has increased. After determination, the specific performance indicators are shown in Table 1 below:

Table 1. Performance parameters of dye absorption spectrum

dye name Maximum absorption wavelength/nm Molar extinction coefficient ε C.I. Disperse Blue 106 613 3631 New Dye 3 599 6856

(5) Product color fastness performance test:

The new dye prepared in this example and C.I. Disperse Blue 106 were applied to the dyeing of spandex and polylactic acid fibers respectively, and their dyeing properties were tested respectively, as shown in Table 2 and Table 3.

Test method: Accurately weigh 0.5000g of new dye and 0.5000g of dispersant NNO, put them into a mortar, add a little water, grind, transfer to a 500ml volumetric flask after 20min, and prepare a dye content of 1g/L Mother liquor, draw this mother liquor to make dye liquors of different concentrations, dye at 110°C for 60 minutes, and obtain a dyeing sample with a 1:1 standard color sample color depth value, using the C1S method in the ISO 105-C06:2010(E) standard The color fastness to washing is measured, the color fastness to dry heat is measured by ISO 105P01:1993, and the fastness to rubbing and light is measured by GB/T3920-2008 and GB/T8427-2008.

Table 2. Comparison of color fastness properties of dyes to spandex dyeing

Table 3. Comparison of color fastness properties of dyes to polylactic acid fiber dyeing

From the experimental data in the above table, it can be seen that the color fastness of the new dye is greatly improved compared with the original dye C.I. Disperse Blue 106, especially the color fastness to various fibers has been greatly improved, reaching the expected assumption The effect shows that the new dye does have a greater affinity to the fiber, and the dye is not easy to migrate out from the inside.

Claims (5)

1. a disperse dye compound, its structural formula as shown in Equation 1:

formula 1.

2. a preparation method for disperse dye compound described in claim 1, is characterized in that, comprises the following steps: select C. I. EX-SF DISPERSE BLUE EX-SF 300 106 dyestuff, carry out linked reaction, prepare described disperse dye compound with dimethyl chloride compound.

3. the preparation method of a kind of disperse dye compound according to claim 2, it is characterized in that: in the three-necked flask of 500ml, add 1.00g to have purified and through vacuum drying C. I. EX-SF DISPERSE BLUE EX-SF 300 106 dyestuff, add the appropriate 300ml methylene dichloride through processed and make solvent, stirring makes dispersed dye dissolve completely, add the triethylamine of 0.61g through processed, accurately take 0.40g dimethyl chloride compound, with appropriate reaction solvent dissolved dilution, in the reactor that slowly instillation is stirred in ice bath, under being warming up to room temperature, react 2-4h; Thin-layer sample application follows the tracks of reaction process, adds 100ml after completion of the reaction containing rare aqueous acid, extracting and separating, is revolved by dye liquor and steams removing dichloromethane solvent, then use appropriate sodium carbonate solution washing and filtering, and clear water washing obtains thick product 1.18g.

4. the preparation method of a kind of disperse dye compound according to claim 3, is characterized in that: the thick product of disperse dye compound of preparation, then through dimethyl formamide recrystallization, obtains disperse dye compound sterling.

5. the purposes of disperse dye compound in spandex or polylactic acid fiber dyeing described in a claim 1.