CN104761923A - A disperse dye compound, and a preparing method and uses thereof - Google Patents

Abstract

A disperse dye compound, and a preparing method and uses thereof are disclosed. The structure formula of the disperse dye compound is shown as a formula 1. The formula 1 is shown in the specification. A C.I. disperse red 1 dye is selected and subjected to a coupling reaction with a dicarbonyl chloride compound to prepare the disperse dye compound. When the disperse dye compound is used for dyeing of polyurethane fibre or polylactic acid fiber, washing fastness and sublimation fastness are obviously improved.

Description

A kind of disperse dye compound and preparation method thereof and purposes

Technical field:

The present invention relates to a kind of Novel disperse dyestuff, refer in particular to a kind of disperse dye compound and preparation method thereof and purposes.

Background technology:

Dispersed dye the earliest for cellulose acetate fibre, after develop rapidly along with the development of trevira (terylene).Present dispersed dye are various in style, chromatogram is complete, can be divided into azo-type, fear quinoid, methine type, ortho-nitrophenyl amine type etc. by structure.Wherein the most noticeable chemical structure is azo, fears quinoid dispersed dye.The dispersed dye of azo-type structure have than advantages such as more complete chromatogram, high Chromaticity intensity (i.e. high molar extinction coefficient), easy manufacture and good economy performance.Fear quinoid dispersed dye and have vividness and the feature such as high colour fastness to light and excellent dyeing behavior, but also there is obvious shortcoming, as lower in coloring intensity and price is more expensive.In recent years, due to heterocyclic dispersed dye bright in color light, coloring intensity is high, fastness ability good, has good hyperchromic effect and higher molar extinction coefficient, and has good dyeing behavior, becomes dyestuff circle and studies a more field.In addition, at exploitation, screening polyester superfine fibre with in dyestuff process, also find that heterocycle dispersed dye have better application performance than other type disperse dye, cause the extensive concern of investigator.The heterocyclic dye synthesized in recent years mainly through introducing the heteroatomss such as nitrogenous, sulphur, oxygen on the diazo component or coupling component of dyestuff, and they are mostly bright in colour, and applicability is strong, has vast potential for future development.

When dispersed dye are a class water-soluble very low, dyeing in water mainly with the non-ionic dye that subparticle be dispersion state existence.According to similar dissolve mutually theory, be mainly used in the dyeing of hydrophobic fibre as fibers such as polyester, polymeric amide and vinegar esters.But because fibrous texture is different, the dyeing behavior that same dyestuff shows on different fiber also has larger difference.At present, according to dyeing behavior and the processing requirement of different fiber, professional quarters screen dispersed dye, obtain the series special dispersed dye being applicable to a certain fiber or a certain technique, and titled with corresponding trade name, to meet the demand in market.

Along with tencel is as polyurethane fiber, acid fiber by polylactic with easily contaminate the appearance such as modified dacron (be called for short ECDP), existing dispersed dye are difficult to meet its dyeing behavior requirement, generally there is the phenomenons such as tinting strength is low, colour fastness is poor, only rely on screening and dyeing to improve and be difficult to tackle the problem at its root.Trace it to its cause, because the second-order transition temperature of these fibers is relatively low, the molecule segment space produced of moving in pars amorpha is more larger, the phenomenon that Yi Jinyi goes out is there is during disperse dyeing, illustrate that existing dispersed dye are large not to the avidity of this fibrid, when causing fiber to be heated, because thermophoresis from inside to outside occurs in dye molecule thermal motion aggravation.Therefore, the resistance to thermal mobility improving dispersed dye has become the study hotspot of current insider.

Summary of the invention:

A first aspect of the present invention object is to provide a kind of novel disperse dye compound, and these dispersed dye, to the dyeing of spandex, acid fiber by polylactic, have significant effect.

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

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

Formula 1.

Above-mentioned disperse dye compound of the present invention, containing two azo dispersion dyes parents and two ester groups (-COO-), the feature of this structure is:

(1), molecular volume and the molecular weight of dyestuff is effectively increased, thus the contact surface added between dyestuff and fiber and Van der Waals force, improve dyestuff to the avidity of fiber.

The upper dye mechanism of dispersed dye shows, dispersed dye rely on Van der Waals force, between hydrogen bond and charge transfer molecular, the reactive force such as power combines with fiber.Van der Waals force size between dyestuff and fiber is decided by the Structure and form of molecule, and and contact area between them and intermolecular distance dependent.The relative molecular mass of general dyestuff is larger, and structure is more complicated, and conjugate system is longer, and line style, coplanarity are better, and is suitable for mutually with the molecular structure of fiber, then Van der Waals force is general larger.

(2), by introducing ester group (-COO-) this characteristic group, hydrogen bond can be formed with the hydrogen group that supplies in fiber, and being suitable for mutually with the structure of trevira.

(3) two independently color bases are contained, change that can not be too large to coloured light generation in, novel disperse dyes structure formula.

A second aspect of the present invention object is to provide a kind of preparation method of aforementioned disperse dye compound, it is characterized in that, comprises the following steps: select C.I. Red-1 200 dyestuff, carry out linked reaction, prepare described disperse dye compound with dimethyl chloride compound.

Further:

In the three-necked flask of 500ml, add 2.50g to have purified and through vacuum drying C.I. Red-1 200 dyestuff, add the appropriate 300ml methylene dichloride through processed and make solvent, stirring makes dispersed dye dissolve completely, add the triethylamine of 1.60g through processed, accurately take 1.00g 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 50ml dilute acid soln after completion of the reaction, 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 2.89g.

The thick product of disperse dye compound of preparation, then through dimethyl formamide recrystallization, obtain disperse dye compound sterling.

A third aspect of the present invention object is to provide the purposes of a kind of aforementioned disperse dye compound in spandex or polylactic acid fiber dyeing, confirm through experiment, adopt above-mentioned disperse dye compound, spandex, acid fiber by polylactic are dyeed, and colour fastness test is carried out to 1:1 standard dyeing sample, test result shows, the washing fastness of spandex and polylactic acid fiber dyeing sample is all comparatively significantly improved, and the fastness to dryheat of spandex tinctorial pattern also improves significantly.

Below in conjunction with the drawings and specific embodiments, the present invention is elaborated further:

Accompanying drawing illustrates:

Fig. 1 is the mass spectrum of disperse dye compound prepared by the embodiment of the present invention;

Fig. 2 is the nucleus magnetic resonance figure of disperse dye compound prepared by the embodiment of the present invention;

Fig. 3 is the Infrared spectroscopy comparison diagram of the disperse dye compound prepared of the embodiment of the present invention and C.I. Red-1 200;

Fig. 4 be the disperse dye compound prepared of the embodiment of the present invention and C.I. Red-1 200 absorption spectrum curve comparison diagram.

Embodiment:

Embodiment 1:

In the three-necked flask of 500ml, add 2.50g to have purified and through vacuum drying C.I. Red-1 200 dyestuff, add the appropriate 300ml methylene dichloride through processed and make solvent, stirring makes dispersed dye dissolve completely, add the triethylamine of 1.60g through processed, accurately take 1.00g 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 50ml dilute acid soln after completion of the reaction, 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 2.89g, and productive rate is 82.59%.

Thick product, again through dimethyl formamide recrystallization, obtains Novel disperse dyestuff pure compounds (hereinafter referred to as reactive monoazo dyestuffs).

Product confirms:

(1), molecular structural formula:

(2), reaction equation:

(3) molecular structure characterization:

Mass spectroscopy: MS (+ESI): m/z (%)=274 (100), 318 (92), 362 (45), 759 (12) [M+H] ⁺.

Nmr analysis: 1H NMR (400MHz, CDCl3) ppm 8.33 (d, J=9.2Hz, 4H), 8.07 (s, 4H), 7.94 (d, J=8.8Hz, 4H), 7.92 (d, J=8.4Hz, 4H), 6.86 (d, J=9.2Hz, 4H), 4.57 (t, J=6.0Hz, 4H), 3.84 (t, J=6.0Hz, 4H), 3.59 (q, J=6.8Hz, 4H), 1.29 (t, J=6.8Hz, 6H).

Infrared spectroscopy: as shown in Figure 3.

Find from Fig. 3: compared with these dispersed dye of C.I. Red-1 200,3200-3500cm in the Infrared spectroscopy figure of reactive monoazo dyestuffs ^-1hydroxyl stretching vibration peak ν is there is not in scope _oH, increased newly and be positioned at 1718cm ^-1the characteristic peak ν at place's ester group (-COO-) _c=O, and other peaks are substantially constant, illustrate that in C.I. Red-1 200, hydroxyl and p-phthaloyl chloride there occurs reaction, generate new disperse dye compound.

(4) spectral absorption performance:

Take 0.01g reactive monoazo dyestuffs, dissolve constant volume at 100mlN, in dinethylformamide, diluting 10 times makes concentration be 0.01g/L, UV-2450 ultraviolet-visible pectrophotometer (Japanese Shimadzu Corporation) is adopted to measure absorption spectrum curve, and compared with same concentrations former dyestuff 0.01g/L C.I. Red-1 200 solution absorption spectra curve.See Fig. 4.

Can find from the absorption spectrum curve figure, compared with C.I. Red-1 200, the maximum absorption wavelength of reactive monoazo dyestuffs offset by 14nm to shortwave direction, become 489nm, and molar extinction coefficient increases to some extent from original 503nm.This is because after dispersed dye coupling, there is the color development system of 2 independent symmetrical in reactive monoazo dyestuffs molecule, and linked together by two ester groups (electron-withdrawing group), reduces the electron donating property of azo component in azo color bodies.Therefore, maximum absorption wavelength is moved to shortwave direction, hypsochromic effect occurs, and molar extinction coefficient increases.After measured, specific performance index is as shown in table 1 below:

Table 1, dye absorber spectrum property parameter

Dyestuff title	Maximum absorption wavelength/nm	Molar extinction coefficient ε
			C.I. Red-1 200	503	3356
Reactive monoazo dyestuffs	489	6595

(5) product fastness properties detects:

The reactive monoazo dyestuffs prepared by the present embodiment, with C.I. Red-1 200, is applied to the dyeing of spandex, acid fiber by polylactic respectively, and tests its dyeing behavior respectively as shown in table 2, table 3.

Testing method: accurately take 0.5000g reactive monoazo dyestuffs and 0.5000g dispersion agent NNO, put into mortar, add little water, grind, after 20min, transfer is settled to the volumetric flask of 500ml, be mixed with the mother liquor that dye content is 1g/L, draw the dye liquor that this mother liquor becomes different concns, dye 60min under 110 DEG C of conditions, obtain the dye sample of 1:1 standard color sample color depth value, C1S method in ISO 105-C06:2010 (E) standard is adopted to measure its Washing, ISO 105P01:1993 is adopted to measure color fastness to dry heat, adopt GB/T3920-2008, GB/T8427-2008 method measures friction and light fastness.

Table 2, dyestuff compare the fastness properties that spandex dyes

Table 3, the dyestuff fastness properties to polylactic acid fiber dyeing compares

From upper table experimental data: reactive monoazo dyestuffs is compared with C.I. Red-1 200, washing fastness for spandex and polylactic acid fiber dyeing sample is all comparatively significantly improved, especially larger to the staining fastness increase rate of various fiber, the fastness to dryheat of spandex tinctorial pattern also improves significantly, illustrate that reactive monoazo dyestuffs has larger avidity to fiber really, dyestuff not easily from internal migration out.

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. Red-1 200 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 2.50g to have purified and through vacuum drying C. I. Red-1 200 dyestuff, add the appropriate 300ml methylene dichloride through processed and make solvent, stirring makes dispersed dye dissolve completely, add the triethylamine of 1.60g through processed, accurately take 1.00g 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 50ml dilute acid soln after completion of the reaction, 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 2.89g.

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.