CN104672949A - Novel reactive blue dye and preparation method thereof - Google Patents
Novel reactive blue dye and preparation method thereof Download PDFInfo
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- CN104672949A CN104672949A CN201410826722.2A CN201410826722A CN104672949A CN 104672949 A CN104672949 A CN 104672949A CN 201410826722 A CN201410826722 A CN 201410826722A CN 104672949 A CN104672949 A CN 104672949A
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Abstract
The invention discloses a novel reactive blue dye and a preparation method of the novel reactive blue dye. The preparation method of the compound comprises the following steps: performing condensation on cyanuric chloride and 2-[2-(4-aminobenzenesul fonamide) ethyl sulfuryl] ethoxyl-sulphating compound and then performing secondary condensation on an obtained condensation compound and 2,4-diaminobenzenesulfonic acid; reducing the temperature of the condensate and performing diazotization; performing acid coupling on the condensate and H acid; then performing alkali coupling on the condensate and diazonium salt of sodium sulfamate or 2,5-disulfonic acid-phenylamine; spraying and drying to obtain a semi-finished product. The reactive blue dye has the characteristics of bright and deep color, high dissoluvability, high compatibility, high elevating power, high fixation rate, high firmness degree of all items and the like; the dye is suitable for coloring, printing and pad-dyeing of cellulosic fibers, protein fibers, viscose fibers and polyamide, and the color fasteness to sunlight and the fastness to rubbing of the novel reactive blue dye are 0.5-1 grade more than those of the general varieties.
Description
Technical field
The present invention relates to technical field of fine, particularly relate to a kind of novel chemically-reactive blue dyes and preparation method thereof.
Background technology
Blue chemically-reactive dyes is one of three primary colors in reactive dyestuffs, main products has C.I active deep blue 194 (active deep blue M-2GE), C.I reactive brilliant blue 19 (reactive blue KN-R), C.I reactive brilliant blue 49 (reactive brilliant blue SPR), C.I reactive brilliant blue 74 (reactive brilliant blue KE-R) etc., although this several blue chromaticity kind can dye and obtain the coloured light of different vividness on cellulosic fibre, but C.I reactive brilliant blue 74 (reactive brilliant blue KE-R) is pale blue, pile-on properties is bad, energy consumption is high, and degree of fixation is low only has 60%; C.I reactive brilliant blue 49 (reactive brilliant blue SPR) can not can only dye as stamp, and coloured light is partially red, degree of fixation 62%-65%; C.I reactive brilliant blue 19 (reactive blue KN-R) obtains the coloured light of different vividness although can dye, because using soda ash or caustic soda vinyl sulfone(RemzaolHuo Xingranliaohuoxingjituan) sulfate ester hydrolysis during fixation, fiber surface is usually caused to occur look flower, color spot, simultaneously higher, the sexual valence ratio of cost, printing and dyeing user is difficult to accept.When active deep blue 194 (the active deep blue M-2GE) of C.I produce, finished product employing is saltoutd obtained, produces a large amount of waste water, contaminate environment; Dyeing colo r light is not bright-coloured, Dry Sack is not dark, and easily detergency difference causes light fastness, abrasion-resistant fastness poor simultaneously.The commodity that this product is output in market, sales volume is maximum, its dye structure is the compound of following formula (1).
Summary of the invention
The object of the invention is the deficiency in order to overcome currently available products certain applications performance, a kind of novel chemically-reactive blue dyes compound is provided.
Another object of the present invention is to provide a kind of preparation method of above-claimed cpd.
A further object of the invention provides above-claimed cpd as a kind of purposes of novel chemically-reactive blue dyes.
Object of the present invention can be reached by following measures: in reactive monoazo dyestuffs structure design, still retain H acid (1-amino-8-naphthol-3,6-disulfonic acid) as coupling component, make it still retain original blue color, cyanuric chloride, vinyl sulfone(RemzaolHuo Xingranliaohuoxingjituan) sulfuric ester are as active group.First to the composition optimizes of the first condensation component vinyl sulfone(RemzaolHuo Xingranliaohuoxingjituan) sulfuric ester, the local structure of condensation component are modified, mainly on hydroxide ethylsulfuric acid ester, introduce the larger sulfoamido of volume, ethyl sulfuryl again, thus carry high molecular hydrophobic and hydrophilic ratio of components, the coplanarity of its molecular structure is significantly declined, thus the substantivity suitably improving dyestuff because of the many good water solubility of sulfonic group but when easily causing dye dark the degree of depth inadequate; Secondly change that acid is even, the even reaction of alkali, the order of condensation reaction and reaction conditions; Above-mentioned two kinds of result products improved are not saltoutd without waste water generation, and improve dye uptake, the degree of fixation of product, improve vividness, light fastness is relative with fastness to rubbing improves 0.5-1 level.
The present invention relates to a series of can as the following compound of the general structure of novel chemically-reactive blue dyes material:
In formula: R=H or SO
3h; M
1, M
2, M
3respective is independently H (form of free acid) or sodium or potassium (form of metal-salt), preferably exists in alkali metal salt.
In above formula, the preferred H or-SO of R
3h.Most preferred two main compound of the present invention, its structure is as follows:
Above-claimed cpd has lovely luster as novel active blue dyes, color is dark, solubleness is high, and compatibleness is good, lifting force is high, degree of fixation is high, the features such as every fastness is excellent.This dyestuff is applicable to the dyeing of cellulosic fibre, protein fibre, viscose fiber and tynex, stamp and pad dyeing, and sun-resistant, fastness to rubbing is higher than the 0.5-1 level of general kind.
A kind of preparation method of formula (I) (IV) compound is: after cyanuric chloride and 2-[2-(4-aminobenzene sulfonamide base) ethyl sulfuryl] ethylene hydroxy sulfuric acid carboxylate condensation and a biquadratic condensation, condenses is lowered the temperature afterwards and hydrochloric acid, Sodium Nitrite carry out diazonium, diazonium and H acid carry out acid even again with to thionamic acid sodium or 2, the saline and alkaline idol of diazonium of 5-disulfonic acid-aniline, dye liquor Direct spraying is dry obtains work in-process.Each coupled reaction diazonium salt must disappear and just can carry out next step reaction.
Wherein 2-[2-(4-aminobenzene sulfonamide base) ethyl sulfuryl] hydroxide ethylsulfuric acid ester mainly adopts p-acetaminobenzenesulfonyl chloride and 2-chloroethyl amine hydrochloride and mercaptoethanol to react the sulfide generated to carry out condensation and obtain thioether, reoxidized by thioether, esterification obtains.All adopt ice to grind diazonium method to the diazonium of thionamic acid sodium, 2,5-disulfonic acid-aniline to prepare, temperature of reaction is 5 ~ 10 DEG C, pH value is 1 ~ 1.5.In the present invention, so-called H acid is the abbreviation of 1-amino-8-naphthol-3,6-disulfonic acid, and two is abbreviations of 2,4-diamino benzene sulfonic acid sodium.
The concrete preparation method of compound (I) is as follows:
Joined by 15.8g Acetanilide in 40-65 DEG C of reaction 2 hours in 128g chlorsulfonic acid, drip 26.7g sulfur oxychloride and react 2 hours, the damp product p-acetaminobenzenesulfonyl chloride of 59g (40%) is filtered to obtain in dilution precipitation.
13.5g2-chloroethylamine hydrochloride is under agitation joined with 8.7g mercaptoethanol solution, regulate pH=4.8, within 4 hours, generate 13.2g beta-hydroxyethyl thioether ethylamine in 55 DEG C of reactions.Be cooled to 0 DEG C, slowly add the damp product p-acetaminobenzenesulfonyl chloride of 59g (40%), regulate pH=3.8, control temperature 0-2 DEG C to react 4 hours, separation, washing obtain 30.7g acetylaminobenzene sulfonamide ethyl-2-hydroxyethyl thioether.
In there-necked flask, add 3.15g sodium wolframate crystal and 6g water, drip the hydrochloric acid of 0.45g30%, adjust pH=5.8.Slowly add 30.7g acetylaminobenzene sulfonamide ethyl-beta-hydroxyethyl thioether, then the hydrogen peroxide dripping 11.2g30% in 1 hour is warmed up to 30-40 DEG C, the soda ash water adjust pH 5-6 of 10%, the hydrogen peroxide dripping 11.4g30% again in 1 hour is warmed up to 50 DEG C, the soda ash water adjust pH 6 of 10%, is finally warmed up to 80 DEG C of reactions and within 8 hours, is oxidized to sulfuryl, acidifying pH=3.5, the 20 DEG C of precipitations of slow temperature, filter to obtain 61.9g acetylaminobenzene sulfonamide ethyl sulfuryl-2-hydroxyethyl tide product.
The sulfuric acid of 9.8g98% is added in esterifier, above-mentioned damp product are added under stirring, open vacuum, slowly be warmed up to 130 DEG C, controlling vacuum tightness size is 0.2-0.3Mpa, react 8 hours terminals to arrive, cooling discharge, pulverize to obtain 40.3g (content is 96.4%) intermediate 2-[2-(4-aminobenzene sulfonamide base) ethyl sulfuryl] hydroxide ethylsulfuric acid ester.
Joined by 18.6g cyanuric chloride in 5g water, 30g ice and pull an oar 1 hour, temperature is less than 0 DEG C; Then 40.3g (content is 96.4%) intermediate 2-[2-(the 4-aminobenzene sulfonamide base) ethyl sulfuryl] hydroxide ethylsulfuric acid ester prepared directly is added, pull an oar and treated that pH was down to 1.2 to 1 hour in 30 minutes, slow 17.6g sodium bicarbonate regulates pH=3-3.5, temperature controls 0 ~ 5 DEG C, the reaction of pH=3-3.5, temperature 0 ~ 5 DEG C is kept to arrive to condensation terminal, survey liquid phase purity simultaneously and reach 95%, prepare secondary condensation.
25.6g (80.2%) 2 is added in the primary condensation liquid that terminal arrives, 4-diamino benzene sulfonic acid sodium industrial goods, add rear stirring 20 minutes, then regulate pH=3.5-4 with 7.5g sodium bicarbonate, be more slowly warming up to 25-35 DEG C, keep pH=3-5.5 with 6.7g sodium bicarbonate simultaneously, keep pH=3-5.5, temperature 25-35 DEG C of reaction 3 is little of the arrival of condensation terminal, and survey liquid phase purity simultaneously and reach 92-93%, chuck cools to 20 DEG C and prepares diazonium.
60g ice is added in the condensated liquid of having lowered the temperature, add 28g30% hydrochloric acid, 6.7g (97%) Sodium Nitrite (being mixed with the sodium nitrite solution of 30%), control temperature 0-5 DEG C, the micro-blue look of KI test paper, congo-red test paper avy blue, sodium nitrite solution adds rear maintenance temperature 0-5 DEG C, the micro-blue colour response of KI test paper 1 hour, eliminates micro-excessive nitrous acid before coupling with a small amount of thionamic acid.
In above-mentioned diazonium salt, directly add 35.7g (85.5%) H acid powder, rinse after stirring with 5g water, temperature is slowly gone up to 15-20 DEG C of reaction and is disappeared to diazonium salt, is cooled to 10 DEG C and treats that alkali is even.
Add in 5g water, 50g ice in the beaker of 500ml, add 16.3g Sodium sulfanilate and 0.2g promotor is pulled an oar 0.5 ~ 1 hour, add 20g ice and be cooled to 5 DEG C, add 28.6g30% hydrochloric acid and 6.68g Sodium Nitrite (being mixed with the sodium nitrite solution of 30%), carry out doazo reaction, control temperature is 5 ~ 8 DEG C of reactions 1 hour, eliminates micro-excessive nitrous acid with a small amount of thionamic acid.
Obtained joining in the even liquid of the acid being cooled to 10 DEG C thionamic acid sodium diazonium salt is carried out alkali occasionally, with sodium bicarbonate adjust ph 6-6.5, temperature 5-8 DEG C of reaction 3 hours; The dry reactive blue dyes obtaining inclined green glow of dye liquor Direct spraying, all concentrates and to obtain work in-process 154g.
The concrete preparation method of compound (IV) is as follows: intermediate is identical with compound (I) to the preparation method of the even part of acid.
Add in 5g water, 50g ice in the beaker of 500ml, add 25.8g2,5-disulfonic acid-aniline and 0.2g promotor are pulled an oar 0.5 ~ 1 hour, add 26g ice and be cooled to 5 DEG C, add 12.6g30% hydrochloric acid and 6.7g Sodium Nitrite (being mixed with the sodium nitrite solution of 30%), carry out doazo reaction, control temperature is 0 ~ 5 DEG C of reaction 1 hour, eliminates micro-excessive nitrous acid with a small amount of thionamic acid.
Obtained 2,5-disulfonic acid-diazonium salt of aniline is joined in the even liquid of the acid being cooled to 10 DEG C and carry out alkali occasionally, with sodium bicarbonate adjust ph 6-6.5, temperature 5 DEG C reaction 3 hours; The dry reactive blue dyes obtaining inclined ruddiness of dye liquor Direct spraying, all concentrates and to obtain work in-process 162g.
The present invention relates to the preparation technology of formula (I) (IV) reactive blue dyes, comprise following reaction: sulfonation reaction, condensation reaction, oxidizing reaction, hydrolysis reaction, esterification, doazo reaction, coupled reaction.
The present invention relates to the condensation reaction condition preparing intermediate 2-[2-(4-aminobenzene sulfonamide base) ethyl sulfuryl] hydroxide ethylsulfuric acid ester: first 2-chloroethyl amine hydrochloride is generated beta-hydroxyethyl thioether ethylamine with mercaptoethanol condensation, improve speed of reaction and transformation efficiency by the temperature, the pH value that change reaction, obtain the thioether that yield does not wait; Beta-hydroxyethyl thioether ethylamine and p-acetaminobenzenesulfonyl chloride condensation generate acetylaminobenzene sulfonamide ethyl-2-hydroxyethyl thioether, consider the stability of its p-acetaminobenzenesulfonyl chloride, speed of reaction and transformation efficiency, determine temperature of reaction 0-2 DEG C, pH=3.5-4, the reaction times, optimize optimum proportioning, technique.
The present invention relates to the oxidation reaction condition of intermediate: constant at sodium wolframate consumption, pH value in reaction 5.5-6.5, temperature 30-85 DEG C, change the proportioning of hydrogen peroxide and acetylaminobenzene sulfonamide ethyl-2-hydroxyethyl thioether, the degree of oxidation of Liquid Detection acetylaminobenzene sulfonamide ethyl-2-hydroxyethyl thioether, the optimum proportioning that control residual quantity obtains hydrogen peroxide can not be less than 2:1; Sodium wolframate consumption is 10% of thioether simultaneously, and catalytic effect is best.
The hydrolysis that the present invention relates to, esterification condition: aniline is hydrolyzed, enzymatic synthesis condition basic simlarity with 4-(2-hydroxyethyl sulfone sulfate), use special esterifier, mol ratio, temperature of reaction, the stirring velocity of adjustment esterification, strengthening mixing effect, liquid phase follow the tracks of the purity of product, control terminal and arrive.
The condensation reaction condition that the present invention relates to: cyanuric chloride and 2-[2-(4-aminobenzene sulfonamide base) ethyl sulfuryl] hydroxide ethylsulfuric acid ester in 0-5 DEG C, pH=3-3.5 carries out primary condensation reaction; Again and a two solid directly carry out secondary condensation, temperature control 25-35 DEG C, pH=3-5.5.
Doazo reaction for the first time: secondary condensation thing cools to 20 DEG C, after salt adding acid out goes out, adds appropriate ice and is cooled to 0-5 DEG C, adds Sodium Nitrite reaction generation first diazo component.
The even reaction conditions of the acid that the present invention relates to: H acid powder is directly joined in the first diazo component, disappears in 15-20 DEG C of reaction to diazonium salt.
Secondary doazo reaction changes traditional method: first Sodium sulfanilate or 2,5-disulfonic acid aniline are dissolved, after salt adding acid out goes out, add appropriate ice and be cooled to 0-5 DEG C, adds sodium nitrite solution and generates diazo component in 0-5 DEG C of reaction.Change Sodium sulfanilate or 2 into, 5-disulfonic acid aniline is that under the condition of 0 DEG C, making beating forms superfine suspensoid at frozen water, add appropriate hydrochloric acid and sodium nitrite solution again and generate diazo component in 5-8 DEG C of reaction, save the consumption of alkali and acid, the obtained diazo component isomery scale of construction is few, few by its obtained reactive blue dyes by-product again, improve its absolute degree of fixation and all other fastness.
The present invention relates to the even reaction conditions of alkali, by changing temperature, pH value, concentration, the alkaline agent of its coupled reaction, use sodium bicarbonate adjust ph, keep low temperature, pH=6-6.5, high density, improve speed of reaction and transformation efficiency, obtain the azoic dyestuff that content does not wait, its azoic dyestuff because of containing isomer number, and produce the different and application performance of absolute degree of fixation and change, optimize optimum proportioning, synthesis obtains the reactive blue dyes more stable than former known activity deep blue M-2GE dyestuff performance.
Positively effect of the present invention is as follows: synthesized reactivity is blue, and dye composition has lovely luster, color is dark, solubleness is high, and compatibleness is good, lifting force is high, degree of fixation is high, the features such as every fastness is excellent.This dyestuff is applicable to the dyeing of cellulosic fibre, protein fibre, viscose fiber and tynex, stamp and pad dyeing, and sun-resistant, fastness to rubbing is higher than the 0.5-1 level of general kind.
Accompanying drawing explanation
Fig. 1 is the technological process of production of reactive blue dyes.
Fig. 2 is the technological process of production of active deep blue M-2GE.
Fig. 3 is the technological process of production of reactive brilliant blue KE-R.
Fig. 4 is the UV comparison diagram of the reactive blue dyes of the deep blue M-2GE of standard activity and embodiment of the present invention gained.
In figure: X-coordinate represents absorbing wavelength nm, ordinate zou Abs represents the dimensionless number of absorbancy.
In figure, lower curve is the UV curve of active deep blue M-2GE, and maximum absorption wavelength is 599nm, and absorption value is 0.677; Top curve is the UV curve of embodiment 1, and maximum absorption wavelength is 611nm, and absorption value is 0.868, and the deep blue M-2GE's of absorption value specific activity is 0.677 high by 28%, and result makes staining power high by 30%.
Embodiment
The following examples describe in further detail of the present invention.
Embodiment 1:
One, the condensation reaction of Intermediate Preparation
Joined by 15.8g Acetanilide in 40-65 DEG C of reaction 2 hours in 128g chlorsulfonic acid, drip 26.7g sulfur oxychloride and react 2 hours, the damp product p-acetaminobenzenesulfonyl chloride of 59g (40%) is filtered to obtain in dilution precipitation.
Two, thioether synthesis
13.5g2-chloroethylamine hydrochloride is under agitation joined with 8.7g mercaptoethanol solution, regulate pH=4.8, within 4 hours, generate 13.2g beta-hydroxyethyl thioether ethylamine in 55 DEG C of reactions.Be cooled to 0 DEG C, slowly add the damp product p-acetaminobenzenesulfonyl chloride of 59g (40%), regulate pH=3.8, control temperature 0-2 DEG C to react 4 hours, separation, washing obtain 30.7g acetylaminobenzene sulfonamide ethyl-2-hydroxyethyl thioether.
Three, sulfide oxidation
In there-necked flask, add 3.15g sodium wolframate crystal and 6g water, drip the hydrochloric acid of 0.45g30%, adjust pH=5.8.Slowly add 30.7g acetylaminobenzene sulfonamide ethyl-beta-hydroxyethyl thioether, then the hydrogen peroxide dripping 11.2g30% in 1 hour is warmed up to 30-40 DEG C, the soda ash water 15g adjust pH 5-6 of 10%, the hydrogen peroxide dripping 11.4g30% again in 1 hour is warmed up to 50 DEG C, the soda ash water 13g adjust pH 6 of 10%, is finally warmed up to 80 DEG C of reactions and within 8 hours, is oxidized to sulfuryl, acidifying pH=3.5, the 20 DEG C of precipitations of slow temperature, filter to obtain 61.9g acetylaminobenzene sulfonamide ethyl sulfuryl-2-hydroxyethyl tide product.
Four, esterification and hydrolysis reaction
The sulfuric acid of 9.8g98% is added in esterifier, above-mentioned damp product are added under stirring, open vacuum, slowly be warmed up to 130 DEG C, controlling vacuum tightness size is 0.2-0.25Mpa, react 8 hours terminals to arrive, cooling discharge, pulverize to obtain 40.3g (content is 96.4%) intermediate 2-[2-(4-aminobenzene sulfonamide base) ethyl sulfuryl] hydroxide ethylsulfuric acid ester.
Five, the condensation reaction of intermediate is prepared
Taking 18.6g cyanuric chloride joins in the beaker of 500ml, and join in 5g water, 30g ice and pull an oar 1 hour, temperature is less than 0 DEG C; Then 40.3g (content is 96.4%) intermediate 2-[2-(the 4-aminobenzene sulfonamide base) ethyl sulfuryl] hydroxide ethylsulfuric acid ester prepared directly is added, pull an oar and treated that pH was down to 1.2 to 1 hour in 30 minutes, slow 17.6g sodium bicarbonate regulates pH=2.5-3.5, temperature controls 0 ~ 5 DEG C, the reaction of pH=3-3.5, temperature 0 ~ 5 DEG C is kept to arrive to condensation terminal, survey liquid phase purity simultaneously and reach 95%, prepare secondary condensation.
Six, two secondary condensation
26.2 (80.2%) 2 are added in the primary condensation liquid that terminal arrives, 4-diamino benzene sulfonic acid sodium industrial goods powder, add rear stirring 20 minutes, add rear stirring 20 minutes, then regulate pH=3.5-4 with 7.5g sodium bicarbonate, slowly be warming up to 25-35 DEG C again, keep pH=3-5.5 with 6.7g sodium bicarbonate simultaneously, keeps that pH=3-5.5, temperature 25-35 DEG C of reaction 3 is little to be arrived up to condensation terminal, survey liquid phase purity simultaneously and reach 92-93%, chuck cools to 20 DEG C and prepares diazonium.
Seven, the diazotization of secondary condensation thing
60g ice is added in the condensated liquid of having lowered the temperature, add 28g30% hydrochloric acid, 7.1g (97%) Sodium Nitrite (being mixed with the sodium nitrite solution of 30%), control temperature 0-5 DEG C, the micro-blue look of KI test paper, congo-red test paper avy blue, sodium nitrite solution adds rear maintenance temperature 0-5 DEG C, the micro-blue colour response of KI test paper 1 hour, eliminates micro-excessive nitrous acid before coupling with a small amount of thionamic acid.
Eight, acid coupling
In above-mentioned diazonium salt, directly add 35.7g (85.5%) H acid powder, rinse after stirring with 5g water, temperature is slowly gone up to 10-15 DEG C of reaction and is disappeared to diazonium salt, is cooled to 10 DEG C and treats that alkali is even.
Nine, the diazotization of Sodium sulfanilate
Add in 5g water, 50g ice in the beaker of 500ml, add 17.8g (100%) Sodium sulfanilate and 0.2g promotor is pulled an oar 0.5 ~ 1 hour, add 20g ice and be cooled to 5 DEG C, add 28.6g30% hydrochloric acid and 7.26g Sodium Nitrite (being mixed with the sodium nitrite solution of 30%), carry out doazo reaction, control temperature is 5 ~ 8 DEG C of reactions 1 hour, eliminates micro-excessive nitrous acid with a small amount of thionamic acid.
Ten, alkaline coupling
Obtained joining in the even liquid of the acid being cooled to 10 DEG C thionamic acid sodium diazonium salt is carried out alkali occasionally, with sodium bicarbonate adjust ph 6-6.5, temperature 5-8 DEG C of reaction 3 hours; The dry reactive blue dyes obtaining inclined green glow of dye liquor Direct spraying, all concentrates and to obtain work in-process 158g.
Embodiment 2:
Step one is identical with embodiment 1 to eight.
Nine, the diazotization of 2,5-diamino benzene sulfonic acids
Add in 5g water, 60g ice in the beaker of 500ml, add 28.3g (100%) 2,5-diamino benzene sulfonic acid and 0.2g promotor are pulled an oar 1 hour, add 30g ice and be cooled to 2 DEG C, add 26g30% hydrochloric acid and 7.3g Sodium Nitrite (being mixed with the sodium nitrite solution of 30%), carry out doazo reaction, control temperature is 3 ~ 5 DEG C of reactions 1 hour, eliminates micro-excessive nitrous acid with a small amount of thionamic acid.
Ten, alkaline coupling
2,5-obtained diamino benzene sulfonic acid diazonium salts are joined in the even liquid of the acid being cooled to 10 DEG C and carry out alkali occasionally, add 10g ice, with sodium bicarbonate adjust ph 7.5-8, temperature 3-5 DEG C of reaction 3 hours; The dry reactive blue dyes obtaining inclined ruddiness of dye liquor Direct spraying, all concentrates and to obtain work in-process 171g.
Embodiment 1 and embodiment 2 work in-process are not saltoutd, and Direct spraying is dried, and non-wastewater discharge, to eco-friendly.
Acetanilide used, 2-chloroethyl amine hydrochloride, mercaptoethanol, hydrogen peroxide, sulfuric acid, H acid (1-amino-8-naphthol-3 in embodiment 1 and embodiment 2,6-disulfonic acid), two (2,4-diamino benzene sulfonic acid sodium), Sodium sulfanilate, 2, the intermediates content of 5-diamino benzene sulfonic acid, hydrochloric acid, Sodium Nitrite, preparation often will criticize Exact Analysis, guarantees that content is errorless.The first five plant the content of raw material and quality to the yield of intermediate 2-[2-(4-aminobenzene sulfonamide base) ethyl sulfuryl] hydroxide ethylsulfuric acid ester and impurities affect larger; Synthesis intermediate 2-[2-(4-aminobenzene sulfonamide base) ethyl sulfuryl] hydroxide ethylsulfuric acid ester purity and content to analyze accurately, otherwise easily cause primary condensation terminal less than, purity is on the low side; The consumption of adjustment Sodium sulfanilate, 2,5-diamino benzene sulfonic acids, the coloured light of fine-tuning product, yield; Lifting force, absolute degree of fixation, rub resistance degree etc. change all to some extent in addition.
Reactive blue dyes synthesized by embodiment 1 and the deep blue M-2GE of activity detect through Shimadzu UV-2400PC spectrophotometer: lower curve is the UV curve of active deep blue M-2GE, and maximum absorption wavelength is 599nm, and absorption value is 0.677; Top curve is the UV curve of embodiment 1, and maximum absorption wavelength is 611nm, and absorption value is 0.868, and the deep blue M-2GE's of absorption value specific activity is 0.677 high by 28%, and result makes staining power high by 30%, and particular case is in table 1 and Fig. 4.
In figure, the reactive blue dyes synthesized by embodiment 1 has following properties compared with the deep blue M-2GE of activity:
Table 1
In the test process of table 1 performance index, have employed following standard:
The general condition regulation that GB/T2374-2007 dyeing measures
The measuring method of GB/T2381-2013 dye and dye intermediate insolubles content
The mensuration of GB/T2386-2006 dye and dye intermediate moisture
The mensuration of GB/T2387-2013 reactive dye coloured light and intensity
The mensuration of GB/T2389-2006 reactive dye hydrolised dye and standard model relative content
The mensuration of GB/T2390-2013 dyestuff pH value
The mensuration of GB/T2391-2006 reactive dye degree of fixation
The measuring method of GB/T3671.1-1996 water-soluble dye solubleness and stability of solution
GB3899.1-2007 dye product nomenclature mo used for textiles
GB3899.2-2007 dye product naming standard used for textiles colour atla
The Determination by instrument of GB/T6688-2008 dyestuff relative intensity and aberration
GB/T8426-1998 textile color stability test colour fastness to light: daylight
GB/T8429-1998 textile color stability test colour fastness to weathering: atmospheric exposure
GB/T8433-2008 textile color stability test colour fastness to chlorinated water (swimming-pool water)
The UV of the deep blue M-2GE of standard activity and the reactive blue dyes of embodiment of the present invention gained contrasts as seen from Figure 4, and concrete numerical value is as shown in table 2.
The UV of the deep blue M-2GE of table 2 standard activity and embodiment 1 gained dyestuff contrasts
Although illustrate and describe embodiments of the invention, for the ordinary skill in the art, to be appreciated that when not departing from principle of the present invention and main raw material and can to carry out multiple proportioning adjustment, condition change to these embodiments, scope of the present invention is by claims and equivalents thereof.
Claims (9)
1. a novel chemically-reactive blue dyes, is characterized in that: the compound structure general formula of this kind of novel chemically-reactive blue dyes is as follows
In formula: R=H or SO
3h; M
1, M
2, M
3respective is independently H or sodium or potassium, exists in alkali metal salt.
2. novel chemically-reactive blue dyes as claimed in claim 1, is characterized in that: the blue dye composition of described reactivity is the mixture of structural formula (I), structural formula (II) and structural formula (III) or the mixture of structural formula (IV), structure formula V and structural formula (VI);
3. prepare novel chemically-reactive blue dyes as claimed in claim 2 for one kind, it is characterized in that, the dixie cup method of this novel chemically-reactive blue dyes comprises: after cyanuric chloride and 2-[2-(4-aminobenzene sulfonamide base) ethyl sulfuryl] ethylene hydroxy sulfuric acid carboxylate condensation and a biquadratic condensation, after condenses cooling diazonium and H acid carry out acid idol again with to thionamic acid sodium or 2, the saline and alkaline idol of diazonium of 5-disulfonic acid-aniline, dye liquor Direct spraying is dry obtains work in-process.
4. novel chemically-reactive blue dyes as claimed in claim 3, it is characterized in that: 2-[2-(4-aminobenzene sulfonamide base) ethyl sulfuryl] hydroxide ethylsulfuric acid ester is reacted by Acetanilide and chlorsulfonic acid, sulfur oxychloride and generates p-acetaminobenzenesulfonyl chloride, react with 2-chloroethyl amine hydrochloride and mercaptoethanol the sulfide generated to carry out condensation and obtain thioether, thioether is reoxidised into sulfuryl, and finally hydrolysis, esterification obtains.
5. novel chemically-reactive blue dyes as claimed in claim 3, is characterized in that: adopt ice mill diazonium to thionamic acid sodium or 2,5-disulfonic acid-aniline diazo component.
6. novel chemically-reactive blue dyes as claimed in claim 5, is characterized in that: the temperature of ice mill diazonium is 5 ~ 10 DEG C, pH value is 0.8 ~ 1.5.
7. novel chemically-reactive blue dyes as claimed in claim 4, is characterized in that: joined by Acetanilide in 40-65 DEG C of reaction 2 hours in chlorsulfonic acid, drip sulfur oxychloride and react 2 hours, damp product p-acetaminobenzenesulfonyl chloride is filtered to obtain in dilution precipitation;
2-chloroethyl amine hydrochloride is under agitation joined in mercaptoethanol solution, regulate pH=4.8, within 4 hours, generate beta-hydroxyethyl thioether ethylamine in 55 DEG C of reactions; Be cooled to 0 DEG C, slowly add damp product p-acetaminobenzenesulfonyl chloride, regulate pH=3.8, control temperature 0-2 DEG C to react 4 hours, separation, washing obtain acetylaminobenzene sulfonamide ethyl-2-hydroxyethyl thioether;
In there-necked flask, add water, sodium wolframate crystal, drip the hydrochloric acid of 30%, adjust pH=5.8; Slowly add acetylaminobenzene sulfonamide ethyl-beta-hydroxyethyl thioether, then the hydrogen peroxide dripping 30% is warmed up to 30-40 DEG C, the soda ash water adjust pH 5-6 of 10%, the hydrogen peroxide dripping 30% is again warmed up to 50 DEG C, the soda ash water adjust pH 6 of 10%, is finally warmed up to 82 DEG C of reactions and within 8 hours, is oxidized to sulfuryl, acidifying pH=3.5, slow cooling 20 DEG C precipitation, filters to obtain acetylaminobenzene sulfonamide ethyl sulfuryl-2-hydroxyethyl tide product;
The sulfuric acid of 98% is added in esterifier, above-mentioned damp product are added under stirring, open vacuum, slowly be warmed up to 130 DEG C, controlling vacuum tightness size is 0.2-0.3Mpa, react 8 hours terminals to arrive, cooling discharge, pulverize to obtain intermediate 2-[2-(4-aminobenzene sulfonamide base) ethyl sulfuryl] hydroxide ethylsulfuric acid ester.
8. novel chemically-reactive blue dyes as claimed in claim 3, it is characterized in that: cyanuric chloride and 2-[2-(4-aminobenzene sulfonamide base) ethyl sulfuryl] hydroxide ethylsulfuric acid ester temperature 0-5 DEG C, pH=3-3.5 carries out primary condensation, reaction 2-3 hour; Twoly between directly adding again carry out secondary condensation, temperature controls 25-35 DEG C, pH=3-5.5, react and arrive terminal in 3 hours; Two contracting things cool to 10 DEG C and add hydrochloric acid, add appropriate ice and are cooled to 2-5 DEG C, add the micro-orchid of 30% sodium nitrite solution KI test paper prepared, and temperature 0-5 DEG C is reacted 1 hour; Directly add H acid powder, react to diazonium salt disappears with 15-20 DEG C, the more saline and alkaline idol of diazonium to thionamic acid sodium or 2,5-disulfonic acid-aniline adding that ice mill diazonium obtains respectively, with sodium bicarbonate adjust ph 6-6.5, temperature is 5-8 DEG C and reacts 3 hours; The dry reactive blue dyes obtaining two kinds of coloured light of dye liquor Direct spraying.
9. novel chemically-reactive blue dyes as claimed in claim 1 or 2, it is characterized in that, this novel chemically-reactive blue dyes is as the purposes of novel chemically-reactive blue dyes, be applicable to the dyeing of cellulosic fibre, protein fibre, viscose fiber and tynex, stamp and pad dyeing, carry out colorant match with reactive orchil and reactive yellow dyes as three primary colors, contaminate different depths, coloured light color.
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