CN104119694A

CN104119694A - Orange reactive dye compound and application

Info

Publication number: CN104119694A
Application number: CN201310454936.7A
Authority: CN
Inventors: 欧其; 王晓红; 汪仁良
Original assignee: ZHEJIANG KEYONG CHEMICAL INDUSTRY Co Ltd
Current assignee: ZHEJIANG KEYONG CHEMICAL INDUSTRY Co Ltd
Priority date: 2013-04-28
Filing date: 2013-09-27
Publication date: 2014-10-29

Abstract

The invention provides an orange reactive dye compound (I) with a hydrazone type structure and an application thereof. The compound not only has excellent perspiration-light fastness but also has extremely high fixation rate, better dye depth and better levelling property and wet processing fastness, and the non-fixation part is easy to wash out. When applied to printing and dyeing of fiber materials, the reactive dye compound has excellent perspiration-light resistance, high dye uptake and fixation rate, good improving property, levelling property and dyeing stability and bright and full color.

Description

A kind of active orange dye compound and application

(1) technical field

The present invention relates to a kind of active orange dye compound, be specifically related to a kind of active orange dye compound and application thereof with hydrazone formula structure.

(2) background technology

The degree of fixation of dyeing and weaving thing on reactive dyestuffs, fastness to wet rubbing is the Focal point and difficult point during printing and dyeing are produced always, generally only 50～80%, cause that on fabric, set dyestuff must be through abundant washing, the removal of soaping, not only cause the wasting of resources, and reduce the particularly wet colour fastness of colour fastness of textiles, and between set dyestuff and cotton fibre, not there is not Intermolecular Forces, after soaping, still have part to remain on fabric, simultaneously, covalent linkage between part reactive dyestuffs and cotton fibre is subject to the impact of ambient conditions, easily there is scission of link hydrolysis, thereby cause the color fastness decreased of DYED FABRICS.

In addition, along with the raising of people to the requirement of textiles ecological, environmental protective performance, sweat proof light fastness to reactive dyestuffs is had higher requirement, because under sweat and daylight dual function, due to the metal ion-chelant of the amino acid in sweat or related substances and metallized dye, make it depart from dye matrix, so just fade or variable color.The dyestuff and the byproduct of reaction thereof that depart from textiles also can directly contact skin, and the safety in utilization of human body is caused to infringement.The problem of cotton reactive dye sweat proof-light fastness is more outstanding at present.

(3) summary of the invention

The object of this invention is to provide a novel active orange dye composition class economy, that there is hydrazone formula structure and application thereof, this compound not only has excellent sweat proof-light fastness, also there is high degree of fixation, preferably depth, preferably level-dyeing property and wet colour fastness, and non-fixing part is easy to eccysis.

The technical solution used in the present invention is:

A kind of active orange dye compound, structure is as shown in formula I:

In formula I:

R ₁, R ₂, R ₃independent is separately H ,-SO ₃m, C ₁～C ₄alkyl or C ₁～C ₄alkoxyl group, is preferably-H ,-SO ₃m ,-CH ₃or-OCH ₃;

Y ₁, Y ₂be-CH=CH independently separately ₂or-C ₂h ₄oSO ₃m, M is H or basic metal, described basic metal is selected from Li, N _aor K, be preferably N _aor K.

Above-claimed cpd (I) structural formula is preferably as follows:

Described compound is preferably one of following formula:

Preferably, in described compound, M is H or Na.

The active orange dye compound of formula I of the present invention, can free acid or preferably prepare with the form of an alkali metal salt, and according to usual method, it can be changed into by free acid form the form of an alkali metal salt.Concrete, described method comprises: first by formula (a) and compound (b) under the existence of hydrochloric acid or sulfuric acid, according to this area ordinary method, carry out respectively diazotization with Sodium Nitrite at 0 DEG C～10 DEG C, gained diazonium compound is carried out coupling with the compound shown in formula (c) again under the condition of pH value 1～7, makes described active orange dye compound;

In formula (a)～(c):

R ₁, R ₂, R ₃independent is separately H ,-SO ₃m, C ₁～C ₄alkyl or C ₁～C ₄alkoxyl group, is preferably-H ,-SO ₃m ,-CH ₃or-OCH ₃; Y ₁, Y ₂be-CH=CH independently separately ₂or-C ₂h ₄oSO ₃m, M is H or basic metal, described basic metal is selected from Li, Na or K.

Preferably, described method can be as follows:

(1) diazotization: after compound (a) is added to and is stirred in water, be cooled to 0～5 DEG C, add hydrochloric acid, making beating 30～90min drips sodium nitrite solution at 0～5 DEG C from liquid level, drip and reaction process in keep Sodium Nitrite micro-excessive.Diazotization, after terminal, is eliminated excessive Sodium Nitrite with thionamic acid, obtains the diazo liquid of compound (a);

(2) diazotization: after compound (b) is added to and is stirred in water, be cooled to 0-5 DEG C, maintain 0-5 DEG C and slowly drip hydrochloric acid and Sodium Nitrite, at this temperature, stir 0.5～3 hour, eliminate excessive Sodium Nitrite with thionamic acid, obtain the diazo liquid of compound (b);

(3) coupling: the diazonium salt of step (1) is joined in the suspension of compound (c), carry out a coupling at 0～10 DEG C.After coupling completes, continue to maintain 0～10 DEG C, slowly add step (2) to react the diazo liquid obtaining, regulating PH is 4～6.8, carries out coupled reaction for the second time, after having reacted, saltouts, is dried, and obtains the dye composition of hydrazone formula structure shown in formula I.

Formula (a)～(c) compound is known dyestuff intermediate, can prepare easily or buy from market.The dye composition of the formula I making can separate in accordance with known methods, for example, use an alkali metal salt (particular certain cancers or sylvite) to saltout, and filters and is dried.

The invention still further relates to described active orange dye compound in the application of preparing in orange active dye.

Utilize the dyestuff finished product that the compounds of this invention is made can be with solid particulate, Powdered or liquid form exists, and conventionally contain the electrolyte salt of common reactive dyestuffs in synthetic, as sodium-chlor, Repone K and sodium sulfate, the dyestuff of solid form also contains the auxiliary agent being common in commercial dyestuff, if by the pH value stabilization of the aqueous solution at 3～7 buffer substance, as Sodium Tetraborate, sodium bicarbonate, Trisodium Citrate, SODIUM PHOSPHATE, MONOBASIC and Sodium phosphate dibasic, and a small amount of siccative, or, if they exist as liquid or the aqueous solution (comprising the common thickening material for the slurry of printing and dyeing).

Reactive dye compound of the present invention, is applicable to the printing and dyeing of cellulosic fibre, tynex and fabric thereof, wherein, the preferred cotton fibre of cellulosic fibre and regenerated fibre, certain vegetative fiber that also can comprise other, as bast-fibre or fabric; Tynex preferably includes skin, hair or silk at interior animal fiber material, and the synthetic filamentary material such as nylon 6, nylon 66.While adopting the above-mentioned filamentary material of active dye printing of the present invention, can carry out in accordance with known reactive dyes dyeing method, as conventional reactive dyestuffs in exhaustion staining and pad dyeing staining, described exhaust dyeing be by textile impregnation in dye liquor, make dyestuff go up gradually the method for dyeing and weaving thing, conventionally need dyed-fixation-washing-soap boiling-washing-dehydration-operations such as oven dry.Described pad dyeing be first textile impregnation in dye liquor, then make fabric pass through roll, dye liquor is evenly rolled into fabric, the dyeing process of processing through decatize or hot melt etc. again, conventionally need be through padding dye liquor-oven dry-(padding fixation liquid)-decatize or bake-wash-soap-wash-operation such as dry.

Conventionally,, due to the difference that on fabric, dyeing pool requires, dyestuff usage quantity also can be different, while using dip method dyeing, dye level is generally 0.1～10%(dyestuff to fabric weight), bath raio 1:2～1:60, preferably 1:10～1:30, just dye 30～60 DEG C of temperature controls, dyeing time 10～30 minutes, 85～95 DEG C of soap boiling temperature, 10～15 minutes soap boiling time, 60～100 DEG C of color fixing temperatures, 10～50 minutes fixation time, fixation pH value 9～11.While using pad dyeing method dyeing, the pick-up of cellulosic fibre is generally 60～80%, 100～103 DEG C of steam temperatures, steaming time 1～3 minute.In pad dyeing method, current more use be cold-rolling heap staining method, dyestuff and alkaline matter are incorporated in pad fix machine, and at room temperature clot banks up and within 2～30 hours, carries out fixation, carry out afterwards thorough rinsing.

Reactive dye compound of the present invention, while being applied to the printing and dyeing of above-mentioned filamentary material, its sweat proof-optical property excellence, dye uptake and degree of fixation are high, and enhancing, level-dyeing property, dye stability are good, and color and luster is vivid full.

(4) brief description of the drawings

Fig. 1 is the embodiment of the present invention 1 compound N MR collection of illustrative plates.

(5) embodiment

Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in this:

Compound with chemical formulation in embodiment writes out with the form of its sodium salt, and this is because they are conventionally prepared and separate with the form of its sodium salt, and is also used for dyeing with the form of sodium salt.The initial compounds described in the following example can free acid form or similarly with the form of its sodium salt for the synthesis of in.

Embodiment 1:

(1) diazotization: after the sulfonation para-ester of 45.5g (being 4-β-ethyl sulfuryl sulfate ester aniline-2-sulfonic acid) is added to and is stirred in 150mL water, the 0-5 DEG C that is cooled on the rocks, add the 31%(w/w of 7.0ml) hydrochloric acid, making beating 30～40min, from liquid level, drip 30.2g30%(w/w at 0～5 DEG C) sodium nitrite solution, keep 5～10 DEG C of temperature, pH=1.0～1.3, stirring reaction 1～3 hour in the situation that potassium iodide starch paper develops the color, in dropping and reaction process, keep Sodium Nitrite micro-excessive, eliminate excessive Sodium Nitrite with thionamic acid, obtain 4-β-ethyl sulfuryl sulfate ester aniline-2-sulfonic acid diazo liquid.

(2) diazotization: after the para-ester of 35.5g (to (beta-hydroxyethyl sulfone sulfate) aniline) is added to and is stirred in 80mL water, the 0-5 DEG C that is cooled on the rocks, maintain 30% the sodium nitrite solution of 0-5 DEG C of 31% hydrochloric acid that slowly drips 14ml and 31g, maintain PH=1.0～1.3, at 0～5 DEG C, stir 2 hours, eliminate excessive Sodium Nitrite with thionamic acid, obtain the diazo liquid of para-ester.

(3) coupling: by 2 of 26.9g, the 4-diamino benzene sulfonic acid stirring to pulp that adds water, slowly add the diazo liquid of step (1), maintain pH1.0～1.3, and control temperature 5-10 DEG C, coupled reaction 3～5 hours, obtain coupling solution one time, sodium bicarbonate is adjusted pH to 5.0～5.5, slowly add step (2) to react the diazo liquid obtaining, the slow adjust pH 6.2～6.6 of sodium bicarbonate, control 10～15 DEG C of temperature and carry out coupling for the second time, coupled reaction 3～5 hours, after having reacted, saltout, dry, the dye composition (seeing Fig. 1 nuclear magnetic resonance map) of hydrazone formula structure shown in main acquisition formula (I-1), and account for total content and be no more than 30%(w/w) the by product of formula (II-1)～(II-2), on this dyestuff, dyeing and weaving thing is hues of orange.

Above-mentioned formula (I-1), (II-1)～(II-2) are sodium-salt form, and M is Na;

The by product of above-mentioned formula (II-1)～(II-2) need not separate especially, can be present in the dyestuff of formula (I-1) jointly painted for filamentary material.

There is absorption peak in spectrum elucidation: 9.4ppm, 9.6ppm and 11.3ppm, should be quinone hydrazone structure, due in about 16ppm without absorption peak, so without intramolecular hydrogen bond; The absorption peak of 5.3ppm phenyl amine H;

There is CH in 3.4-4.0ppm ₂absorption peak; 7.5-8.5ppm is 8 H on phenyl ring and former phenyl ring.

Embodiment 2～8:

According to the preparation method described in embodiment 1 or similar method, different: to adopt respectively the arylamine in the arylamine 1, arylamine 2 alternative steps (1), step (2) of equimolar amount in table 1 to carry out diazotization, can make hydrazone formula dyestuff as shown in table 1, upper dyeing and weaving thing presents bright orange.

Table 1

Application Example:

At 60 DEG C, respectively 100 grams of cotton fabrics are added in the dye bath of 1500 grams of 45g/L sodium-chlor and 2 grams of reactive dyestuffs compositions that obtain according to embodiment 1～8.At this temperature, dye after 45 minutes, add the sodium carbonate solution of 20g/L, keep this temperature to dye again 45 minutes.Then, rinse product dyed thereby, soap 15 minutes with nonionic detergent, post rinse is also dry, records its basic dyeing behavior eigenwert in table 2:

Table 2: basic dyeing characteristic value S.E.R.F

Project	S value	E value	F value	R value
					Embodiment 1	51.4%	97.0%	88.3%	75.9%
Embodiment 2	51.1%	96.9%	88.1%	75.4%
					Embodiment 3	50.6%	96.1%	86.5%	74.2%
Embodiment 4	51.7%	97.7%	87.5%	75.9%
					Embodiment 5	52.0%	98.2%	89.8%	76.5%
Embodiment 6	50.6%	96.4%	86.2%	75.0%
					Embodiment 7	49.8%	94.6%	85.2%	73.7%
Embodiment 8	52.2%	98.6%	90.3%	77.0%

In upper table:

S value represents the size of dyestuff to fiber affinity.S value is large, shows that dyestuff is large to the avidity of fiber, inhales look fast, but migration property meeting variation, easily washing property is poor to dye rear unconjugated dyestuff.

E value represents the degree of exhaustion of dyestuff.E value is large, represents that the clean absorption rate of dyestuff is high, and the utilization ratio of general remark dyestuff is high, and depth is good, and the pollution level of dyeing waste is little.

F value represents the degree of fixation of dyestuff.F value is large, illustrate to generate with fiber that covalent linkage reacts and the dyestuff of set is many, and dyestuff and unreacted dyestuff that generation is hydrolyzed is few, and dye utilization rate is high.

The reactive height of R value representation dyestuff.R value is large, illustrates that dyestuff is strong with the ability that fiber generation covalent linkage reacts under alkaline condition, and speed of reaction is fast, but the too high aberration end to end that easily causes.

From above-mentioned table 1, reactive dyestuffs S value of the present invention and R value are moderate, illustrate that avidity and level-dyeing property are all good; E value and F value are large, illustrate that dyestuff depth is good, and degree of fixation is high, and dye utilization rate is high.

In addition, test by method definite in GB/T3921, GB/T3920 and GB/T14576 respectively that it is water-fastness, antifriction scrape along sweat proof-photorecombination colour fastness, the results are shown in Table 3:

Table 3: colour fastness

To sum up, hydrazone formula structure-activity dyestuff of the present invention, while being applied to dyeing, has preferably comprehensive dyeing behavior, and depth is good, degree of fixation is high, level-dyeing property is good, wet colour fastness is excellent.

Claims

1. an active orange dye compound, structure is as shown in formula I:

In formula I:

R ₁, R ₂, R ₃independent is separately H ,-SO ₃m, C ₁～C ₄alkyl or C ₁～C ₄alkoxyl group; Y ₁,

Y ₂be-CH=CH independently separately ₂or-C ₂h ₄oSO ₃m, M is H or basic metal.

2. compound as claimed in claim 1, is characterized in that described compound is one of following formula:

3. compound as claimed in claim 1 or 2, is characterized in that in described compound, M is H, Na or K.

4. compound as claimed in claim 1 is in the application of preparing in orange active dye.