CN102942804A - Reactive dye and preparation method of aqueous preparation of the reactive dye - Google Patents

Abstract

The invention provides a reactive dye. The reactive dye has a general formula shown in the patent specification. Through introduction of a vinylsulfonyl amino group into an azo dye, the reactive dye improves electronic absorption of a dye, keeps an activity in a good level, and is more stable. Molecules of the reactive dye are introduced with water soluble groups and monovalent cation groups so that water-solubility of the reactive dye is improved. The invention also provides a preparation method of an aqueous preparation of the reactive dye. The preparation method comprises that a vinylsulfonyl sulfate group-containing dye undergoes a degreasing reaction under alkaline conditions and reaction products and an active amino compound undergo an addition reaction to produce the aqueous preparation of the reactive dye. The preparation method has the advantages of simple processes, easily controlled conditions and good feasibility.

Description

The preparation method of chemically-reactive dyes and aqueous formulation thereof

Technical field

The present invention relates to preparation of dyestuff technique, particularly the preparation method of a kind of chemically-reactive dyes and aqueous formulation thereof.

Background technology

Textiles is digital ink-jet printed develop in recent years very fast, with respect to traditional printing technique, can save the making of printing screen, save great amount of cost and time, reduced issuable waste water in a lot of traditional stamps, quantity for changeable colored type and order is also unrestricted, can be described as the printing technique that is adapted to the New Times fully.

See technically, digital ink-jet printed is that aqueous formulation with the special active dyestuff is mixed with ink, by the direct spray printing of ink-jet printer on textiles, the aqueous formulation of the reactive dyestuffs powder dye of comparing, as long as its concentration is enough high, more easily prepare ink for printing, also reduced the dust pollution in the dyestuff dissolution process.

Therefore, for weaving digit printing ink, how to provide a kind of stability in storage good, colorant dissolubility is outstanding, and is applicable to digital ink-jet printed dyestuff, is a problem to be solved of the present invention.

Summary of the invention

One of purpose of the present invention is to provide a kind of chemically-reactive dyes, the good stability of its standing storage, and solubleness is good, can be applicable to digital ink-jet printed.

Chemically-reactive dyes of the present invention has the structure suc as formula general formula shown in the I:

Wherein, R1 is H or organic straight chain;

R2 is azo structure contained color bodies;

V is the organic chain that 2-4 carbon atom consists of;

X is water soluble group;

M is monovalent cation.

The present invention has introduced the ethene sulfuryl in azo dyes, this is because the strong electrophilic of ethene sulfuryl, make the carbon-carbon double bond activation of ethene sulfuryl, cloud density reduces on the beta carbon, easily is subject to the attack of nucleophilic reagent Mierocrystalline cellulose negative ion, and nucleophilic addition occurs, generate ehter bond between dyestuff and fiber after the reaction, but this reaction is reversible, and in the dyeing course, the meeting of ethene sulfuryl and steeping in water for reconstitution are given birth to side reaction simultaneously, generate oxyethyl group sulfone type dye, on the other hand, because the electrophilic of ethene sulfuryl is stronger, cause pigment stability not good, based on this kind situation, the present invention has also introduced substituted-amino in the ethene sulfuryl, become the vinyl sulfone(RemzaolHuo Xingranliaodehuoxingjituan) aminoderivative, drawn a nitrogen-atoms on the sulfuryl after, reduced the electrophilic of sulfuryl, and making activity decreased, dyestuff become more stable, storge quality is greatly improved.

X is water soluble group in the dye molecule, and M is monovalent cation.

R1 in the dye molecule is H or organic straight chain, and this allows the molecule linearity of dyestuff increase, and the affinity of dyestuff and fiber increases.

Preferably, described R2 has the following formula structure:

This expression, chemically-reactive dyes of the present invention is preferably following structure:

Among formula a, formula b and the formula c, R all refers to R1 group of the present invention.

Preferably, R1 is the alkyl chain of H, 1 ~ 4 carbon atom formation or the heterocycle chain that contains the groups such as sulphur, carbonyl, alcohol, sulfonic acid and phosphoric acid, and described alkyl chain or heterocycle chain can better improve hydrophilicity and the dye stability of dyestuff.

Preferably, V is the alkyl chain of 2 ~ 4 carbon atoms formations or the chain that comprises covalent linkage, and M is H, Na or Li.

Two of the object of the invention is to provide the preparation method of described chemically-reactive dyes, comprises the steps:

The dyestuff that (1) will contain the vinyl sulfone(RemzaolHuo Xingranliaodehuoxingjituan) sulfate group carries out the degreasing reaction under alkaline condition, obtain vinyl-sulfone reactive dyes, as shown in the formula (1):

(2) vinyl-sulfone reactive dyes is under pH=9 ~ 10 and 85 ~ 95 ℃ of conditions of temperature, with active amino compound generation addition reaction, as shown in the formula (2):

Need to prove that active amino compound of the present invention refers to that main chain is carbochain, contain at least amino more than one, and possess the compound of reactive behavior.In addition, in use allow to add the conventional auxiliary agent of an amount of dye field at preparation dyestuff of the present invention, comprise urea (3-10%), Virahol (0.1-5%), ethylene glycol (1-15%), Diethylene Glycol (1-20%), diethylene glycol monobutyl ether (0.5-8%), trolamine (0.01-1%), glycerine (0.1-5%) and tensio-active agent (0.1-1%) etc., auxiliary dosage all accounts for the percentage calculation of dyestuff gross weight by its weight.

Beneficial effect of the present invention:

In sum, than prior art, the good stability of chemically-reactive dyes standing storage provided by the invention, solubleness is good; Method technique of the present invention is simple, and condition is easily controlled, and easily implements.

Figure of description

Fig. 1 is the structural representation that circulation groove 1 that the present invention adopts is connected with circulation groove 2

Embodiment

The present invention is described in further detail below in conjunction with embodiment.But this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following embodiment, all technology that realizes based on content of the present invention all belong to scope of the present invention.

One, preparing product

Embodiment 1

Be the dyestuff (from C.I.Reactive Yellow 145) of (I-1) with the 32kg structural formula; be dissolved in the 900kg pure water in 20 ℃; adding the 8kg tertiary sodium phosphate regulates about pH to 9.5; add the 13kg N-methyltaurine after stable; be warming up to 90 ℃; be incubated 10 minutes, then use 60% vinegar acid for adjusting pH to 6, namely obtain structural formula and be a(see above state) dyestuff.

Among the formula a

R(is R1 group of the present invention) be methyl;

V is the organic chain that 2 carbon atoms consist of;

X is sulfonic group.

Embodiment 2

Be the dyestuff (from C.I.Reactive Red 195) of (II-1) with the 35kg structural formula; be dissolved in the 900kg pure water in 20 ℃; adding the 7kg tertiary sodium phosphate regulates about pH to 9.5; add the 10kg N-methyltaurine after stable; be warming up to 85 ℃; be incubated 10 minutes, then use 60% vinegar acid for adjusting pH to 6, namely obtain the dyestuff that structural formula is b.

Among the formula b

R(is R1 group of the present invention) be methyl;

V is the organic chain that 2 carbon atoms consist of;

X is sulfonic group.

Embodiment 3

Be the dyestuff (from C.I.Reactive Black 5) of (III-1) with the 40kg structural formula; be dissolved in the 940kg pure water in 20 ℃; adding the 9kg tertiary sodium phosphate regulates about pH to 9.5; add the 15kg N-methyltaurine after stable; be warming up to 90 ℃; be incubated 10 minutes, then use 50% vinegar acid for adjusting pH to 6, namely obtain the dyestuff that structural formula is c.

Among the formula c

R(is R1 group of the present invention) be methyl;

V is the organic chain that 2 carbon atoms consist of;

X is sulfonic group.

Preparation M is the dyestuff of Li:

The dye structure formula (a) and (b) that obtain among the embodiment 1,2,3, the dyestuff of (c) are dissolved in respectively in the circulation groove 1, the lithium chloride solution of preparation 5% in circulation groove 2, open simultaneously pump 1 and pump 2, circulated 10 hours, can obtain M is three kinds of dyestuffs of Li.

Fig. 1 intermediate ion exchange membrane is the anion-modified composite membrane of process, and film has repulsive interaction to negatively charged ion, and positively charged ion is had adsorption, and when can make cationic exchange like this, negatively charged ion can not see through ionic membrane.

Two, the solubility property of test implementation example product.

Testing method:

The dyestuff with structural formula I-1, II-1, III-1 and a, b, c of above-described embodiment gained is dried to powdery by medium-sized spray drying device, wherein structural formula is that M is Li in the molecule of dyestuff of a, b, c, then powder is mixed with respectively the solution of different concns, strength of solution sees the following form 1.

Again the solution that configures is placed magnetic agitation, be warming up to 50 ℃ and be incubated 30 minutes, the solution after insulation is processed filters with qualitative filter paper, and drains moisture content with vacuum pump, whether again the filter paper of draining is placed air drying, observing the filter paper surface has dyestuff remaining.

Test result sees Table 1

Table 1

Observe the result in the table 1, the solubleness of dyestuff (I), (II), (III) obviously is better than the solubleness of dyestuff (I-1), (II-1), (III-1), when concentration reaches 300g/L, still have fabulous solvability, be fit to very much the ink of configuration high density.

Three, test implementation example aging of product performance and stability in storage

Each embodiment product is concentrated into solid content in nanofiltration equipment be 25% aqueous formulation, and regulate pH to 7.5, again with in the sealed vessel of packing into behind the cellulose acetate membrane filtration of water soluble dyestuffs with 0.45 μ m.

After the water soluble dyestuffs of sealing placed in 60 ℃ of baking ovens baking 48h, with the filterableness of the cellulose acetate filter membrane test baking front and back of 0.45 μ m, and measure its pH value.

With the sealing ink place respectively 1 day, 5 days, 10 days, 30 days, 90 days after, test respectively filterableness with the cellulose acetate filter membrane of 0.45 μ m, and measure its pH value.

Test result sees Table 2

Table 2

Data from table 2 can obtain, and dyestuff (I), (II), (III) are behind the senile experiment through 60 ℃ of baking 48h, and filterableness is still very outstanding, and pH is also invariable.And depositing under the normal temperature state after for 3 months, still have good strainability and constant pH value.

Need to prove at last; above embodiment only is used for technical scheme of the present invention is described and unrestricted; although with reference to preferred embodiment technical scheme of the present invention is had been described in detail; those skilled in the art are to be understood that; can make amendment or be equal to replacement technical scheme of the present invention; and not breaking away from aim of the present invention and scope, it all should be encompassed in the middle of protection scope of the present invention.

Claims (5)

1. chemically-reactive dyes is characterized in that: have the structure suc as formula general formula shown in the I:

Wherein, R1 is H or organic straight chain;

R2 is azo structure contained color bodies;

V is the organic chain that 2-4 carbon atom consists of;

X is water soluble group;

M is monovalent cation.

2. according to right 1 described chemically-reactive dyes, it is characterized in that: described R2 has the following formula structure:

3. chemically-reactive dyes according to claim 1 and 2 is characterized in that: R1 is the alkyl chain that consists of of H, 1 ~ 4 carbon atom or the heterocycle chain that contains the groups such as sulphur, carbonyl, alcohol, sulfonic acid and phosphoric acid.

4. chemically-reactive dyes according to claim 3 is characterized in that: V is the alkyl chain that consists of of 2 ~ 4 carbon atoms or the chain that comprises covalent linkage, and M is H, Na or Li.

5. prepare the method for described chemically-reactive dyes aqueous formulation, it is characterized in that: comprise the steps:

The dyestuff that (1) will contain the vinyl sulfone(RemzaolHuo Xingranliaodehuoxingjituan) sulfate group carries out the degreasing reaction under alkaline condition, obtain vinyl-sulfone reactive dyes, as shown in the formula (1):

(2) vinyl-sulfone reactive dyes is under pH=9 ~ 10 and 85 ~ 95 ℃ of conditions of temperature, with active amino compound generation addition reaction, as shown in the formula (2):

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