CN105585874A - Gray reactive dye and preparation method thereof - Google Patents
Gray reactive dye and preparation method thereof Download PDFInfo
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- CN105585874A CN105585874A CN201511006222.5A CN201511006222A CN105585874A CN 105585874 A CN105585874 A CN 105585874A CN 201511006222 A CN201511006222 A CN 201511006222A CN 105585874 A CN105585874 A CN 105585874A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
- C09B62/04—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a triazine ring
- C09B62/08—Azo dyes
- C09B62/095—Metal complex azo dyes
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Abstract
The invention discloses a preparation method of gray reactive dye. 4-nitro-2-aminophenol diazonium and H acid have an alkaline coupling reaction, the pH value is controlled to be larger than 6.5, and the mixture reacts for 10 h at the temperature of 0-5 DEG C; a coupling body and chromium trichloride have a metal complex reaction under the action of a catalyst at the temperature of 95-100 DEG C, and the residual amount of free chromium metal is controlled; tricyanogen chloride and 3 times of ammonia water have a primary condensation reaction, ice water is added to a condensation product, washing is performed twice, and ammonium chloride is removed; the primary condensation product and a complexing solution have a secondary condensation reaction; finally, a dispersant NNO and a dispersant MF are added for standardization, and a gray reactive dye product is obtained through filtering, impurity removal and spray drying.
Description
Technical field
The invention belongs to reactive dye preparation field, be specifically related to the preparation side of the active gray dyes of a kind of metal complexMethod.
Background technology
C.I.ReactiveBlack8 belongs to metal complex type dye, and dyestuff contains crome metal, or metallic cobalt, or metalThe mixture of chromium and cobalt, gray after dying on cellulosic fabric, is black when consumption reaches 80-100g/L, be used for fabricDirect printing, difference is dyed material good compatibility, is widely used in the toning component of various colors. On market product mainly withThe compound that contains crome metal and cobalt is composite, or only containing metal chrome dye and orchil are composite to standard items look by a certain percentageLight.
Traditional synthesis technique is that 4-nitro-Ortho-Aminophenol diazol and H acid solution carry out alkaline coupling, and color base is saltoutdRefining, after making beating, carry out metal complex with chromium sulfate, sodium acetate or chromium sulfate, liquid caustic soda, then with Cyanuric Chloride carry out primary condensation,Finally add ammoniacal liquor to carry out secondary condensation, finally add that sodium chloride and potassium chloride are saltoutd, isolated by filtration, dry gained. Tradition workSkill is through the 2 roads technique of saltouing, and without except ammonia operation, has that product salt condensate rate is large, product solubility is low to moderate 20g/L, Dry Sack is inadequateThe inferior position such as deeply, receipts amount is low.
This product, under dyestuff technical research person makes joint efforts, was obtained larger breakthrough in recent years, and publication number is CNThe Chinese patent application of 101538413A discloses a kind of production technology that cleans of reactive black K-BR, this production technology operationAs follows: 4-nitro-Ortho-Aminophenol diazol and H acid to be carried out to alkaline coupling, chromium sulfate and sodium acetate for the coupling solution obtainingOr cobaltous sulfate and liquid caustic soda carry out metal complex, after color base that complexing is good is cooling, be neutralized to pH for neutral, simultaneously by Cyanuric ChlorideCarry out primary condensation to free ammonia mass concentration≤1% with sulfonic acid or the formic acid derivates of aniline, the primary condensation thing obtaining addsThe complexing color base that enters cooling neutralization carries out secondary condensation, and secondary condensation liquid is processed the dry dyestuff one-tenth that obtains of then spraying through filmProduct.
The method, by improving color base synthetic technology, is omitted the color base salting-out procedures of traditional handicraft; With the sulfonic acid of aniline orFormic acid derivates substitutes ammoniacal liquor, more than the solubility of raising product reaches 100g/L, must on color depth, have a certain upgrade; FortuneWith membrane technology, product strength is reached more than 150%, omit final step finished product salting-out procedures. The method makesProduct adopts the sulfonic acid of aniline or formic acid derivates to substitute ammoniacal liquor, and unreacting material is difficult for removing, and the coloured light of dyestuff is had necessarilyImpact.
Along with the enhancing of people to environmental consciousness, not only textile is proposed to more and more higher quality requirements, also require" three wastes " in manufacture textile process are fewer and feweri. This product also exists improving performance poor at present, and Integ value is dark not, spinsThe residual Cr of fabric fabric6+Exceed standard up to tens times, solubility does not still reach other and dyes the problems such as material 200g/L.
Summary of the invention
The invention provides a kind of preparation method of active gray dyes, the active gray dyes of preparation is applied to cotton, brocadeWhen the dyeing of synthetic fibre, silk, wool fabric and stamp, there is good dyefastness, particularly in dyeing process, have goodSolubility, free Cr6+Remain in and on fabric, be less than 2ppm, dye with other that material compatibility is good, stamp and reproducibility good.
A preparation method for active gray dyes, comprises the following steps:
(1), under the condition existing at hydrochloric acid, 4-nitro-Ortho-Aminophenol and natrium nitrosum carry out diazo-reaction, obtainDiazonium salt solution;
(2) H acid is carried out coupling reaction with the diazonium salt solution that step (1) obtains, and obtains coupling solution;
(3) under the effect of catalyst, coupling solution and chromium trichloride that step (2) obtains carry out complex reaction, and complexing is completeCheng Houjing processes and obtains complex liquid later;
Described catalyst comprises at least one in salicylic acid and phthalic anhydride;
Described H acid is 1:(0.4～0.47 with the mol ratio of chromium trichloride);
(4) Cyanuric Chloride is pulled an oar in frozen water, then add polyacrylamide dispersant, continue to stir 5～10 pointsClock, carries out primary condensation reaction, after reacting completely, obtains primary condensation liquid through processing later;
(5) complex liquid that the primary condensation liquid that step (4) obtains and step (3) obtain carries out consecutive condensation, obtainsReactant liquor in to add dispersant NNO and Dispersant MF to spray dry, obtain described active gray dyes.
The structural formula of described active gray dyes is as follows:
Its Chinese style (I) is (40-60) with formula (II) mol ratio: 10.
In the present invention, by adopting incomplete complexing technology, avoid excessive free chromium residues, in complexation process, addCatalyst, makes free chromium be reacted into complexing body with zygosome more up hill and dale; Moreover in order to improve solubility and the product of dyestuffStorage stability, reduce the residual quantity of ammonium salt, in technique, adopt ammoniacal liquor and Cyanuric Chloride one contracting technology, utilize product to be insoluble toThe character of water removes ammonium chloride, adds specific dispersant simultaneously, then obtains slurry with the condensation of chromium complex liquid, finally by crossing markStandardization, the dry finished product that obtains of spraying.
As preferably, in step (1), the mol ratio of described hydrochloric acid, natrium nitrosum and 4-nitro-Ortho-Aminophenol is(1.5～2.0)：(1.0-1.05)：1。
As preferably, in step (2), H acid is first dissolved into 20% neutral aqueous solution with lithium hydroxide, then adds little SuBeat, and then carry out coupling reaction with diazonium salt solution;
The mol ratio of described sodium bicarbonate and H acid is (0.9～1.2): 1. Now, by control reaction system pH value withReaction temperature, reduces the activity at the amino ortho position of H acid, improves the coupling yield at hydroxyl ortho position, makes the zygosome that purity is higher.
As preferably, in step (3), described catalyst is the mixture of salicylic acid or salicylic acid and phthalic anhydride, and catalyst is usedAmount is the 5-10% of chromium trichloride quality.
As preferably, in step (3), first with hydrochloric acid, coupling solution solution is adjusted to 4.5～5.0, and then described in addingCatalyst and chromium trichloride heat up and carry out complex reaction.
As preferably, in step (3), described post processing comprises: with lithium hydroxide control reacting liquid pH value at 11.5-12.5 continue to stir 3～5 hours, are then cooled to 30-35 DEG C, add 30% phosphoric acid adjust pH little in 7.0-7.5 reaction 3～5Time, filter and obtain complex liquid. Now, by increasing phosphoric acid dechromisation operation, can further reduce the residual of free chromium, effectivelyEnsure that free chromium can be controlled at below certain value.
As preferably, in step (4), the temperature of primary condensation reaction is 20-25 DEG C.
As preferably, in step (4), described last handling process is as follows: add frozen water to expand volume to three times of original volumes, enterRow dilution, stratification, extracts upper strata with self priming pump and contains ammonium chloride supernatant, repeats for several times, to obtain lower floor's primary condensation product.
As preferably, in step (1)～(5), described 4-nitro-Ortho-Aminophenol, H acid, Cyanuric Chloride, ammoniacal liquor moleThan being (0.95～1.05): 1:(1.05～1.15): (2.5～3.5).
As preferably, in step (5), described dispersant NNO and the weight ratio of Dispersant MF are 20～40:60～80,The polymerization degree n of dispersant NNO and Dispersant MF is independently selected from 3～4.
The concrete preparation process of these reactive dye is as follows:
(1) 4-nitro-Ortho-Aminophenol is dissolved in quantitative hydrochloric acid solution, moltenly starts to drip 30% natrium nitrosum after clearSolution, dropping temperature and reaction temperature are all controlled at below 25 DEG C, reaction time 60-90 minute;
(2) H acid is dissolved into 20% neutral solution with lithium hydroxide, and amount on the rocks equates with the end water yield, adds sodium bicarbonate, stirsMix in a moment, the diazol that step (1) is prepared slowly adds, and pH value is greater than more than 6.5 all the time, temperature 0-5 DEG C of reaction 10More than hour;
(3) the color base solution that step (2) obtains is warming up to 60 DEG C, with 30% hydrochloric acid adjustment color base pH value of solution=4.5-5.0,Add salicylic acid, continue to be warming up to 100 DEG C, add chromium trichloride solid, maintain 95-100 DEG C of reaction 3 hours, use 15% hydrogen-oxygenChange lithium solution and slowly add, control pH value and continue reaction 3 hours at 11.5-12.5;
(4) step (3) temperature is reduced to 30-35 DEG C, adds 30% phosphoric acid adjust pH in 7.0-7.5 reaction 3 hours, mistakeElimination, except insoluble impurities and sediment, is collected filtrate;
(5) Cyanuric Chloride disperses making beating 1 hour in frozen water, adds polyacrylamide dispersant, continues to stir 5 minutesAdd fast afterwards ammoniacal liquor, control temperature at 20-25 DEG C of reaction 1.5-2 hour, add frozen water to expand 3 times of volumes and dilute, leave standstillLayering, extracts upper strata with self priming pump and contains ammonium chloride supernatant; Expand 3 times of dilutions of volume with frozen water for the second time again, stratification, goesExcept supernatant, obtain lower floor's primary condensation product;
(6) in step (5) primary condensation, join fast above-mentioned step (4) filtrate that has been warming up to 50-55 DEG C, use simultaneously15% lithium hydroxide solution maintains pH value between 6.5-7.5, reaction 16-20 hour, then adjust pH value 8.5-9.5 and react 4 littleTime, returning between adjust pH 7.5-8.0 with 30% phosphoric acid, the reactant liquor obtaining and dispersant NNO and Dispersant MF carry out standardization,Spraying is dry, obtains described active gray dyes.
Compared with prior art, the active gray dyes tool that prepared by the present invention has the following advantages:
(1) have good solubility, storage-stable is good;
(2) float is had to good covering, its compatibility, stamp favorable reproducibility;
(3) printing and dyeing expect that upper residual free chromium can reach Oeko-Tex standard, meets environmental requirement below;
(4) higher degree of fixation, improving performance, every fastness ability brilliance;
Detailed description of the invention
Embodiment 1
In diazonium still, add 1500L, be warming up to 40 DEG C, add 158 kilograms of 30% hydrochloric acid and 154 kilograms of 4-nitro-2-ammoniaBase phenol, stir 30 minutes molten clear after, start to drip 230 kilograms of 30% sodium nitrite solutions, dropping temperature and reaction temperature are allBe controlled at below 25 DEG C, reaction time 60-90 minute, eliminates excessive natrium nitrosum with sulfamic acid;
In coupling still, add end water 1700L, add 341 kilograms of H acid, stir after 20 minutes and dissolve H with 20% lithium hydroxideAcid, pH value is controlled at 7.0-7.5, and molten clear rear 1700 kilograms and 85 kilograms of sodium bicarbonate on the rocks, stir in a moment, and step (1) is madeThe diazol of getting ready slowly adds, and pH value is greater than more than 6.5 all the time, and temperature 0-5 DEG C of reaction is more than 10 hours;
Coupling terminal to after be warming up to 60 DEG C, with 30% hydrochloric acid adjust pH=4.5-5.0, add 10 kilograms of salicylic acids, continueContinue and be warming up to 100 DEG C, add the chromium trichloride solid of 120 kg with the crystallization water, maintain 95-100 DEG C of reaction 3 hours, use15% lithium hydroxide solution slowly adds, and controls pH value and continues reaction 3 hours at 11.5-12.5; Complexing terminal to after be reduced to30-35 DEG C, adds 30% phosphoric acid adjust pH 7.0-7.5 reaction 3 hours, and filtering and impurity removing, collects filtrate, is transferred to secondary condensationStill;
Primary condensation still adds end water 500L and 500 kilograms of ice, drops into 200 kilograms of Cyanuric Chlorides and in frozen water, disperses making beating1 hour, add 5 kilograms of PAMCs (molecular weight 600～8,000,000, ion degree 10～50%), continue to stir 5 pointsAfter clock, add fast 280 kilogram of 20% ammoniacal liquor, control temperature at 20-25 DEG C of reaction 1.5-2 hour, add frozen water to expand volume extremely4000L, stratification, extracts upper strata with self priming pump and contains ammonium chloride supernatant; Expand volume to 4000L with frozen water for the second time again,Stratification, removes supernatant, obtains lower floor's primary condensation product;
In secondary condensation kettle, complex liquid is warming up to 50-55 DEG C, in primary condensation thing, joins fast in complex liquid, uses simultaneously15% lithium hydroxide solution maintains pH value between 6.5-7.5, reaction 16-20 hour, then use 15% lithium hydroxide solution adjustmentPH value 8.5-9.5 reaction 4 hours, returns between adjust pH 7.5-8.0 with 30% phosphoric acid, adds 200 kilograms of dispersant NNO and 500Kilogram Dispersant MF carries out standardization, filters, spraying is dry, obtains 1800 kilograms of active grey finished product dyestuffs.
Embodiment 2
In diazonium still, add 1500L, be warming up to 40 DEG C, add 158 kilograms of 30% hydrochloric acid and 154 kilograms of 4-nitro-2-ammoniaBase phenol, stir 30 minutes molten clear after, start to drip 230 kilograms of 30% sodium nitrite solutions, dropping temperature and reaction temperature are allBe controlled at below 25 DEG C, reaction time 60-90 minute, eliminates excessive natrium nitrosum with sulfamic acid;
In coupling still, add end water 1700L, add 341 kilograms of H acid, stir after 20 minutes and dissolve H with 20% lithium hydroxideAcid, pH value is controlled at 7.0-7.5, and molten clear rear 1700 kilograms and 90 kilograms of sodium bicarbonate on the rocks, stir in a moment, and step (1) is madeThe diazol of getting ready slowly adds, and pH value is greater than more than 6.5 all the time, and temperature 0-5 DEG C of reaction is more than 10 hours;
Coupling terminal to after be warming up to 60 DEG C, with 30% hydrochloric acid adjust pH=4.5-5.0, add 12.5 kilograms of phthalic anhydrides, continueContinue and be warming up to 100 DEG C, add 125 kilograms of chromium trichloride solids with the crystallization water, maintain 95-100 DEG C of reaction 3 hours, use15% lithium hydroxide solution slowly adds, and controls pH value and continues reaction 3 hours at 11.5-12.5; Complexing terminal to after be reduced to30-35 DEG C, adds 30% phosphoric acid adjust pH 7.0-7.5 reaction 3 hours, and filtering and impurity removing, collects filtrate, is transferred to secondary condensationStill;
Primary condensation still adds end water 500L and 500 kilograms of ice, drops into 200 kilograms of Cyanuric Chlorides and in frozen water, disperses making beating1 hour, add 5 kilograms of PAMCs (molecular weight 600～8,000,000, ion degree 10～50%), continue to stir 5 pointsAfter clock, add fast 280 kilogram of 20% ammoniacal liquor, control temperature at 20-25 DEG C of reaction 1.5-2 hour, add frozen water to expand volume extremely4000L, stratification, extracts upper strata with self priming pump and contains ammonium chloride supernatant; Expand volume to 4000L with frozen water for the second time again,Stratification, removes supernatant, obtains lower floor's primary condensation product;
In secondary condensation kettle, complex liquid is warming up to 50-55 DEG C, in primary condensation thing, joins fast in complex liquid, uses simultaneously15% lithium hydroxide solution maintains pH value between 6.5-7.5, reaction 16-20 hour, then use 15% lithium hydroxide solution adjustmentPH value 8.5-9.5 reaction 4 hours, returns between adjust pH 7.5-8.0 with 30% phosphoric acid, adds 250 kilograms of dispersant NNO and 450Kilogram Dispersant MF carries out standardization, filters, spraying is dry, obtains 1800 kilograms of active grey finished product dyestuffs.
Embodiment 3
In diazonium still, add 1500L, be warming up to 40 DEG C, add 158 kilograms of 30% hydrochloric acid and 154 kilograms of 4-nitro-2-ammoniaBase phenol, stir 30 minutes molten clear after, start to drip 230 kilograms of 30% sodium nitrite solutions, dropping temperature and reaction temperature are allBe controlled at below 25 DEG C, reaction time 60-90 minute, eliminates excessive natrium nitrosum with sulfamic acid;
In coupling still, add end water 1700L, add 341 kilograms of H acid, stir after 20 minutes and dissolve H with 20% lithium hydroxideAcid, pH value is controlled at 7.0-7.5, and molten clear rear 1700 kilograms and 80 kilograms of sodium bicarbonate on the rocks, stir in a moment, and step (1) is madeThe diazol of getting ready slowly adds, and pH value is greater than more than 6.5 all the time, and temperature 0-5 DEG C of reaction is more than 10 hours;
Coupling terminal to after be warming up to 60 DEG C, with 30% hydrochloric acid adjust pH=4.5-5.0, add 5 kilograms of salicylic acids and 5 public affairsJin phthalic anhydride, continues to be warming up to 100 DEG C, adds 115 kilograms of chromium trichloride solids with the crystallization water, maintains 95-100 DEG C of reaction 3Hour, slowly add with 15% lithium hydroxide solution, control pH value and continue to react 3 hours at 11.5-12.5; After complexing terminal arrivesBe reduced to 30-35 DEG C, add 30% phosphoric acid adjust pH 7.0-7.5 reaction 3 hours, filtering and impurity removing, collects filtrate, is transferred to twoInferior condensation kettle;
Primary condensation still adds end water 500L and 500 kilograms of ice, drops into 200 kilograms of Cyanuric Chlorides and in frozen water, disperses making beating1 hour, add 5 kilograms of PAMCs (molecular weight 600～8,000,000, ion degree 10～50%), continue to stir 5 pointsAfter clock, add fast 280 kilogram of 20% ammoniacal liquor, control temperature at 20-25 DEG C of reaction 1.5-2 hour, add frozen water to expand volume extremely4000L, stratification, extracts upper strata with self priming pump and contains ammonium chloride supernatant; Expand volume to 4000L with frozen water for the second time again,Stratification, removes supernatant, obtains lower floor's primary condensation product;
In secondary condensation kettle, complex liquid is warming up to 50-55 DEG C, in primary condensation thing, joins fast in complex liquid, uses simultaneously15% lithium hydroxide solution maintains pH value between 6.5-7.5, reaction 16-20 hour, then use 15% lithium hydroxide solution adjustmentPH value 8.5-9.5 reaction 4 hours, returns between adjust pH 7.5-8.0 with 30% phosphoric acid, adds 150 kilograms of dispersant NNO and 550Kilogram Dispersant MF carries out standardization, filters, spraying is dry, obtains 1800 kilograms of active grey finished product dyestuffs.
Embodiment 1～3 is prepared respectively to active gray dyes sample, the reactive black K-BR synthetic with traditional handicraft on marketAfter skill upgrading, obtained in recent years the good active black P-N of quality and compare (CN101538413A), table 1 contrast is dissolvedDegree, the Integ value under different depth, coloured light and degree of fixation (coloured light is taking black P-N as standard); Table 2 contrast printing and dyeing can on expecting belowExtracting metals chromium; Table 3 contrasts every fastness.
Table 1
Table 2
Table 3
Claims (10)
1. a preparation method for active gray dyes, is characterized in that, comprises the following steps:
(1), under the condition existing at hydrochloric acid, 4-nitro-Ortho-Aminophenol and natrium nitrosum carry out diazo-reaction, obtain diazoniumSalting liquid;
(2) H acid is carried out coupling reaction with the diazonium salt solution that step (1) obtains, and obtains coupling solution;
(3), under the effect of catalyst, coupling solution and chromium trichloride that step (2) obtains carry out complex reaction, after complexing completesObtain complex liquid through post processing;
Described catalyst comprises at least one in salicylic acid and phthalic anhydride;
Described H acid is 1:(0.4～0.47 with the mol ratio of chromium trichloride);
(4) Cyanuric Chloride is pulled an oar in frozen water, then add polyacrylamide dispersant, continue to stir 5～10 minutes, enterRow primary condensation reaction, obtains primary condensation liquid through processing later after reacting completely;
(5) complex liquid that the primary condensation liquid that step (4) obtains and step (3) obtain carries out consecutive condensation, and what obtain is anti-Answer that in liquid, to add dispersant NNO and Dispersant MF to spray dry, obtain described active gray dyes.
2. the preparation method of active gray dyes according to claim 1, is characterized in that, in step (1), and described saltThe mol ratio of acid, natrium nitrosum and 4-nitro-Ortho-Aminophenol is (1.5～2.0): (1.0-1.05): 1.
3. the preparation method of active gray dyes according to claim 1, is characterized in that, in step (2), H acid first withLithium hydroxide is dissolved into 20% neutral aqueous solution, then adds sodium bicarbonate, and then carries out coupling reaction with diazonium salt solution;
The mol ratio of described sodium bicarbonate and H acid is (0.9～1.2): 1.
4. the preparation method of water-soluble active gray dyes according to claim 1, is characterized in that, in step (3), and instituteState the mixture that catalyst is salicylic acid or salicylic acid and phthalic anhydride, catalyst amount is the 5-10% of chromium trichloride quality.
5. the preparation method of water-soluble active gray dyes according to claim 1, is characterized in that, in step (3), firstCoupling solution solution is adjusted to 4.5～5.0 with hydrochloric acid, and then adds described catalyst and chromium trichloride to heat up to carry out complexing anti-Should.
6. the preparation method of water-soluble active gray dyes according to claim 1, is characterized in that, in step (3), and instituteThe post processing of stating comprises:, be then cooled to 11.5-12.5 continuation stirring 3～5 hours with lithium hydroxide control reacting liquid pH value30-35 DEG C, adds 30% phosphoric acid adjust pH 7.0-7.5 reaction 3～5 hours, filters and obtains complex liquid.
7. the preparation method of water-soluble active gray dyes according to claim 1, is characterized in that, in step (4), and oneThe temperature of inferior condensation reaction is 20-25 DEG C.
8. the preparation method of water-soluble active gray dyes according to claim 1, is characterized in that, in step (4), and instituteThe last handling process of stating is as follows: add frozen water to expand volume to three times of original volumes, dilute, stratification, extracts with self priming pumpAmmonium chloride supernatant is contained on upper strata, repeats for several times, to obtain lower floor's primary condensation product.
9. the preparation method of active gray dyes according to claim 1, is characterized in that, in step (1)～(5), and institute4-nitro-Ortho-Aminophenol, H acid, Cyanuric Chloride, the ammoniacal liquor mol ratio stated are (0.95～1.05): 1:(1.05～1.15):(2.5～3.5)。
10. the preparation method of active gray dyes according to claim 1, is characterized in that, in step (5), describedThe weight ratio of dispersant NNO and Dispersant MF is 20～40:60～80, and the polymerization degree n of dispersant NNO and Dispersant MF independentlyBe selected from 3～4.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108559306A (en) * | 2018-05-18 | 2018-09-21 | 无锡润新染料有限公司 | A kind of grey dyestuff cleanly production technique of the activity for the stamp can be used for people cotton |
| CN109575630A (en) * | 2018-11-20 | 2019-04-05 | 浙江劲光实业股份有限公司 | A kind of preparation method of rufous reactive dye |
| CN114752229A (en) * | 2022-04-11 | 2022-07-15 | 黄山普米特新材料有限公司 | Reactive grey dye |
| CN114752229B (en) * | 2022-04-11 | 2024-07-05 | 黄山普米特新材料有限公司 | Reactive grey dye |
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| US3484432A (en) * | 1965-07-23 | 1969-12-16 | Ici Ltd | Water-soluble,reactive 1:2-cobalt azo dyestuffs containing halogeno or sulpho-s-triazine groups |
| CN101538413A (en) * | 2009-04-02 | 2009-09-23 | 无锡润新染料有限公司 | Active black K-BR and nonpolluting production technology thereof |
| CN102031018A (en) * | 2010-11-19 | 2011-04-27 | 无锡润新染料有限公司 | Composite reactive grey for printing and dyeing and clean production process thereof |
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| US3484432A (en) * | 1965-07-23 | 1969-12-16 | Ici Ltd | Water-soluble,reactive 1:2-cobalt azo dyestuffs containing halogeno or sulpho-s-triazine groups |
| CN101538413A (en) * | 2009-04-02 | 2009-09-23 | 无锡润新染料有限公司 | Active black K-BR and nonpolluting production technology thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108559306A (en) * | 2018-05-18 | 2018-09-21 | 无锡润新染料有限公司 | A kind of grey dyestuff cleanly production technique of the activity for the stamp can be used for people cotton |
| CN109575630A (en) * | 2018-11-20 | 2019-04-05 | 浙江劲光实业股份有限公司 | A kind of preparation method of rufous reactive dye |
| CN114752229A (en) * | 2022-04-11 | 2022-07-15 | 黄山普米特新材料有限公司 | Reactive grey dye |
| CN114752229B (en) * | 2022-04-11 | 2024-07-05 | 黄山普米特新材料有限公司 | Reactive grey dye |
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