CN1059688C - Reactive dye for medium temp. dying with high colour fixation rate and method for synthesizing same - Google Patents

Reactive dye for medium temp. dying with high colour fixation rate and method for synthesizing same Download PDF

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Publication number
CN1059688C
CN1059688C CN 96116228 CN96116228A CN1059688C CN 1059688 C CN1059688 C CN 1059688C CN 96116228 CN96116228 CN 96116228 CN 96116228 A CN96116228 A CN 96116228A CN 1059688 C CN1059688 C CN 1059688C
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reactive
dye
dyestuff
high colour
reactive dye
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CN1134961A (en
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朱正华
江利民
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SHANGHAI REACTIVE DYES UNITED INST
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SHANGHAI REACTIVE DYES UNITED INST
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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
    • C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
    • C09B62/503—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring the reactive group being an esterified or non-esterified hydroxyalkyl sulfonyl or mercaptoalkyl sulfonyl group, a quaternised or non-quaternised aminoalkyl sulfonyl group, a heterylmercapto alkyl sulfonyl group, a vinyl sulfonyl or a substituted vinyl sulfonyl group, or a thiophene-dioxide group

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Abstract

The present invention discloses reactive dye for medium temperature dying with the high color fixation rate and a synthetic method thereof. The dye adopts two color bases and two divinyl sulphone active groups, the two color bases and the two divinyl sulphone active groups are connected by a bridged group, and macromolecular reactive dye is formed. Therefore, the dye uptake of the reactive dye is increased, the color fixation rate of the reactive dye is from 90 to 95%, and the technical progress of reactive dye industry is greatly impelled. In addition, the synthetic method of the dye is simple and convenient, the yield of products is high, and the large-scale industrial preparation can be realized.

Description

Temperature dyeing reactive dyestuffs and synthetic method thereof in a kind of high colour-fast rate
The invention belongs to the reactive dyestuffs field, relate to temperature dyeing reactive dyestuffs and synthetic method thereof in a kind of high colour-fast rate.
It is complete that reactive dyestuffs have formed a cover chromatogram through the development of four more than ten years, lovely luster, wet fastness excellent dye type.For a long time, dyeing is being pursued the high colour-fast rate (degree of fixation～100%) of dyestuff always, and it also is the target that the dyestuff worker dreams of.Reduce the printing and dyeing cost because high colour-fast rate not only means, and mean and alleviate or eliminates coloured sewage of printing and dyeing.But weigh reactive dyestuffs with this target of high colour-fast rate, its shortcoming especially severe that seems, because existing commodity reactive dyestuffs, the highest degree of fixation only is about 70%, general all about 50%, therefore dyeing expects that urgently the dyestuff scientific worker provides the reactive dyestuffs of high colour-fast rate of new generation, to overcome the above-mentioned shortcoming of existing reactive dyestuffs.Many for this reason dyestuff workers are constantly making great efforts developing.Look back the development history of reactive dyestuffs: by the reactive dyestuffs of initial single active group, as: Procion X type (dichloro s-triazine type), Remazol type (Vinyl-Sulfone Type), develop into the reactive dyestuffs that contain double active base, as M type (chloro-s-triazine and vinyl sulfone(Remzaol mixed type), Procion HE type is KE type (a two chloro-s-triazine type), make the degree of fixation of reactive dyestuffs be increased to 70% by 50%, the visible double-active group of introducing in reactive dyestuffs is a kind of effective ways that improve degree of fixation.
For this reason, two class dyestuffs more than we have investigated in the laboratory, find:
(1) Procion HE type is KE type reactive dyestuffs, must therefore need much energy consumption in 85 ℃ of dyeing (belonging to the high temperature dyeing type), and the dyeing cost is increased, and even so, the degree of fixation of KE type reactive dyestuffs also has only about 70%.
(2) M type reactive dyestuffs, owing to adopt a chloro-s-triazine and vinyl sulfone(Remzaol as two active groups, its dyeing temperature can be reduced to about 60 ℃, but investigate discovery through our laboratory, M type reactive dyestuffs direct bad, promptly their dye uptake is not high, has caused their degree of fixation not high.In addition, the best color fixing temperature of one chloro-s-triazine must be about 85 ℃, and the best color fixing temperature of vinyl sulfone(Remzaol is about 60 ℃, therefore M type reactive dyestuffs are when reality dyes, can not bring into play the maximum utility of two active groups simultaneously, so can not reach higher degree of fixation, so its degree of fixation only is 60-70%.
European patent 0226774A in 1987, a kind of reactive dyestuffs that contain two ethene sulfuryls are disclosed, the feature of this reactive dyestuffs is that two vinyl sulfone(Remzaol active group nationalitys help a triazine ring to be connected with a dye matrix, the dye matrix that is a part need consume bimolecular vinyl sulfone(Remzaol active group, vinyl sulfone(Remzaol active group consumption as important intermediate increases, and certainly will increase the cost of dyestuff like this.And the synthesis technique more complicated, so do not see that so far industrialized report is arranged.
The objective of the invention is to overcome the above-mentioned shortcoming of prior art, on the basis of a large amount of experiments, provide temperature dyeing reactive dyestuffs and synthetic method thereof in a kind of high colour-fast rate, the degree of fixation of reactive dyestuffs is increased to more than 90% for branch of industry.
Design of the present invention is such: the contriver is engaged on the reactive dyestuffs research work experiential basis at many decades, shortcoming at the prior art existence, imagine a kind of reactive dyestuffs with novel texture, in their molecular structure, have two color bases and two vinyl sulfone(Remzaol active groups, couple together by abutment, constitute macromolecular reactive dyestuffs, expectation increases the substantivity of dyestuff by the molecular weight that increases dyestuff, improve the dye uptake of dyestuff, thereby reach the purpose of the degree of fixation that improves reactive dyestuffs, and reduce the production cost of dyestuff significantly, thereby promote the technical progress of reactive dyestuffs industry greatly.
The present invention is achieved in that the present invention adopts two color bases, and two vinyl sulfone(Remzaol active groups get up by two triazine ring bridgings, constitute macromolecular reactive dyestuffs.Its general structure is as follows: Wherein: R 1, R 2Can be-H ,-OCH 3,-Cl;
D 1, D 2Be the dye matrix part, the two can be identical, also can be different, and they can be respectively azos, containing metal azo, anthraquinone, phthalocyanine, or a kind of among the first ;
B is an abutment, and it can be NH, NHNH, NHCH 2CH 2NH,
Figure C9611622800042
Or
Figure C9611622800043
In a kind of.
In addition, the invention also discloses a kind of reactive dyestuffs synthetic method, solved on the three polychlorostyrene hydrogen rings difficulty in the 3rd chlorine atom and the light ethyl sulfonyl aniline sulfuric ester condensation reaction, found a kind of control that is easy to, the method of condensing that the product yield is high can be realized large-scale industrial production.
Specific implementation method of the present invention:
1. at first KE type reactive dyestuffs (industrial raw material or by existing method synthetic KE type dye) are added water and be mixed with solution, feed intake in mixing reactor with the aqueous solution of hydroxyethyl sulfone aniline sulfuric ester (industrial raw material) mol ratio again, mix by 1: 2.
2. regulate the pH=3-7 of said mixture then, at temperature 90-100 ℃ of following condensation reaction 1-3 hour, regulate the pH=6-6.5 of system then with weak base, and adding sodium-chlor is saltoutd, make temperature dyeing reactive dyestuffs in the said high colour-fast rate of the present invention, wherein said weak base can be a kind of in yellow soda ash, salt of wormwood, the sodium phosphate, and the pH value of condensation reaction the best is preferably 4.5-6.
Condensation reaction is shown below:
According to above-mentioned synthetic method, can make warm painted reactive dyestuffs in the following various high colour-fast rate, its structural formula is as follows:
Reactive brilliant red dyestuff (1)
Figure C9611622800053
Reactive brilliant red dyestuff (2)
Figure C9611622800061
Reactive brilliant red dyestuff (3)
Reactive brilliant red dyestuff (4)
Reactive brilliant red dyestuff (5)
Figure C9611622800064
Reactive brilliant red dyestuff (6)
Figure C9611622800071
Active scarlet dye (7)
Figure C9611622800072
Active scarlet dye (8)
Figure C9611622800073
Reactive brilliant red dyestuff (9)
Figure C9611622800074
Reactive brilliant red dyestuff (10)
Figure C9611622800081
Reactive brilliant red dyestuff (11)
Figure C9611622800082
Reactive brilliant red dyestuff (12)
Figure C9611622800083
Active light yellow dye (13)
Figure C9611622800084
Active light yellow dye (14)
Active light yellow dye (15)
Yellow reactive dyes (16)
Figure C9611622800093
Yellow reactive dyes (17)
Figure C9611622800094
Yellow reactive dyes (18)
Yellow reactive dyes (19)
Figure C9611622800102
Yellow reactive dyes (20)
Figure C9611622800103
Yellow reactive dyes (21)
Figure C9611622800104
Yellow reactive dyes (22)
Figure C9611622800111
Yellow reactive dyes (23)
Figure C9611622800112
Active orange dye (24)
Figure C9611622800113
Active orange dye (25)
Figure C9611622800114
Active orange dye (26)
Figure C9611622800121
Active orange dye (27)
Figure C9611622800122
Active orange dye (28)
Figure C9611622800123
Reactive dark blue dyestuff (29)
Figure C9611622800124
Reactive dark blue dyestuff (30)
Figure C9611622800131
Reactive dark blue dyestuff (31)
Reactive dark blue dyestuff (32)
Figure C9611622800133
Reactive dark blue dyestuff (33)
Figure C9611622800134
Reactive dark blue dyestuff (34)
Reactive turquoise blue dyestuff (35)
Reactive blue dye (36)
Reactive brilliant bule dyestuff (37)
Figure C9611622800144
Reactive brilliant bule dyestuff (38)
Reactive brilliant bule dyestuff (39)
Figure C9611622800152
Reactive dark blue dyestuff (40)
Figure C9611622800153
Active green dye (41)
Reactive violet dyestuff (42)
Active palm dye (43)
Further illustrate content of the present invention below in conjunction with embodiment:
Embodiment 1
Synthesizing of high colour-fast rate reactive brilliant red dyestuff of the present invention (1):
A. the reaction formula of building-up process:
Figure C9611622800162
B. synthetic method:
Get 30 gram reactive brilliant red KE-3B (0.02mol) in 250 milliliters of there-necked flasks, dissolve with 120 ml waters, add between 15 grams-80 ml water solution of beta-hydroxyethyl sulfuryl aniline sulfuric ester (0.041mol), mix under the room temperature, pH value with dilute hydrochloric acid adjusting said mixture is 5-5.5 then, under agitation be warming up to 95 ℃ of reactions 1.5 hours, disappear until the KE type dye, be cooled to room temperature, it is 6.5 that the aqueous sodium carbonate with 15% is regulated the pH value, adds 45 gram sodium-chlor again, continue to stir 1 hour, till analysing clearly to dyestuff, filter, drip NaH on the filter cake 2PO 4Solution number droplet, and in 80 ℃ dry down, purple pulverulent solids 35 grams (intensity 100%), this product yield of the present invention is 87.5%.
Measure according to GB2391-80, dye uptake is 96.0%, and degree of fixation is 91.2%.
The degree of fixation of reactive brilliant red KE-3B is 77.12%, and synthetic reactive brilliant red dyestuff of the present invention (1) specific activity bright red KE-3B degree of fixation improves 14.08%.
Embodiment 2
Synthesizing of high colour-fast rate active scarlet dye of the present invention (8):
A. the reaction formula of building-up process:
Figure C9611622800171
B. synthetic method:
Get 3.8 gram cyanuric chlorides (0.0206mol), an amount of ice, place 400 ml beakers, stirring to pulp 30 minutes adds 6.4 gram 1-amino-8-naphthols-3, (the H-acid of 6-disulfonic acid, 0.02mol) 40 ml water solution, be 3 at pH, under the 8-10 ℃ of condition reaction 3-5 hour, disappear to free amine group, filter, in filtrate, add 7.4 grams 4,4 '-diaminobenzil-2, (the D.S.D. acid of 2 '-disulfonic acid base, 0.02mol) 40 ml water solution, regulating pH with 15% aqueous sodium carbonate under the room temperature is 6, is warming up to 40 ℃ of reactions 2 hours, cooling, stand-by.
Get 3.7 gram cyanuric chlorides (0.02mol) again, an amount of ice, place 400 ml beakers, stirring to pulp 30 minutes adds 4.8 gram 2-amino-5-naphthols-7-sulfonic acid (J-acid, 50 ml water solution 0.02mol), at pH is 3.5, reaction is 3 hours under the 3-5 ℃ of condition, to the free amine group disappearance, in its impouring said mixture, regulating the pH value under the room temperature is 6.5, reacted 3 hours down in 40-45 ℃, disappear, add diazonium salt (0.04mol) solution of 3.7 gram aniline until free amine group, at pH is 6-6.5,5-8 ℃ of following coupling 5 hours, disappearing to diazonium salt is terminal point, makes the KE type dye.
Add between 15 grams-80 ml water solution of beta-hydroxyethyl sulfuryl aniline sulfuric ester (0.041mol), mix under the room temperature, the pH value with dilute hydrochloric acid adjusting said mixture is 5-5.5 then, under agitation is warming up to 95-100 ℃ of reaction 2.5 hours, disappear until the KE type dye, be cooled to room temperature, it is 6.3 that the aqueous sodium carbonate with 15% is regulated the pH value, adds 40 gram sodium-chlor again, continue to stir 1 hour, till analysing clearly to dyestuff, filter, filter cake drips NaH 2PO 4Solution number droplet, and in 80 ℃ dry down, red powder shape solid 36.5 grams (intensity 100%), this product yield of the present invention is 91.25%.
Measure according to GB2391-80, dye uptake is 97.03%, and degree of fixation is 92.68%.
The degree of fixation of the bright red KE-3G of similar activity is 77.9%, and the bright red KE-3G degree of fixation of synthetic active scarlet dye of the present invention (8) specific activity improves 14.78%.
Embodiment 3
Synthesizing of high colour-fast rate Yellow reactive dyes of the present invention (18):
A. the reaction formula of building-up process:
Figure C9611622800181
B. synthetic method:
Get 39 gram reactive yellow KE-4R (0.02mol) in 250 milliliters of there-necked flasks, dissolve with 120 ml waters, add between 15 grams-80 ml water solution of beta-hydroxyethyl sulfuryl aniline sulfuric ester (0.041mol), mix under the room temperature, pH value with dilute hydrochloric acid adjusting said mixture is 4.5-5 then, under agitation be warming up to 90-95 ℃ of reaction 3 hours, disappear until the KE type dye, be cooled to room temperature, it is 6.5 that the aqueous sodium carbonate with 15% is regulated the pH value, adds 45 gram sodium-chlor again, continue to stir 1 hour, till analysing clearly to dyestuff, filter, filter cake drips NaH 2PO 4Solution number droplet, and in 80 ℃ dry down, purple pulverulent solids 43 grams (intensity 100%), this product yield of the present invention is 93.5%.
Measure according to GB2391-80, dye uptake is 96.4%, and degree of fixation is 90.61%.
The degree of fixation of reactive yellow KE-4R is 73.5%, and the yellow KE-4R degree of fixation of synthetic Yellow reactive dyes of the present invention (18) specific activity improves 17.11%.
Embodiment 4
Synthesizing of high colour-fast rate reactive dark blue dyestuff of the present invention (29):
A. the reaction formula of building-up process:
Figure C9611622800191
B. synthetic method:
Get 29 gram Reactive blue KE-R (0.02mol) in 250 milliliters of there-necked flasks, dissolve with 100 ml waters, add between 15 grams-80 ml water solution of beta-hydroxyethyl sulfuryl aniline sulfuric ester (0.041mol), mix under the room temperature, pH value with dilute hydrochloric acid adjusting said mixture is 5.2-5.6 then, under agitation be warming up to 100 ℃ of reactions 1.5 hours, disappear until the KE type dye, be cooled to room temperature, it is 6 that the aqueous sodium carbonate with 15% is regulated the pH value, adds 50 gram sodium-chlor again, continue to stir 1 hour, till analysing clearly to dyestuff, filter, filter cake drips NaH 2PO 4Solution number droplet, and in 80 ℃ dry down, mazarine pulverulent solids 36 grams (intensity 100%), this product yield of the present invention is 94.7%.
Measure according to GB2391-80, dye uptake is 99.6%, and degree of fixation is 95.42%.
The degree of fixation of Reactive blue KE-R is 78.4%, and the blue KE-R degree of fixation of synthetic reactive dark blue dyestuff of the present invention (29) specific activity improves 17.02%.

Claims (3)

1. temperature dyeing reactive dyestuffs in the high colour-fast rate is characterized in that such dyestuff has following general structure: Wherein: R 1, R 2Can be-H ,-OCH 3,-Cl;
D 1, D 2Be the dye matrix part, the two can be identical, also can be different, and they can be respectively azos, containing metal azo, anthraquinone, phthalocyanine, or a kind of among the first ;
B is NH, NHNH, NHCH 2CH 2NH,
Figure C9611622800022
Or
Figure C9611622800023
In a kind of.
2. the synthetic method of temperature dyeing reactive dyestuffs in the high colour-fast rate, it is characterized in that: will two chloro-s-triazine type dyes and the aqueous solution of hydroxyethyl sulfone aniline sulfuric ester be to feed intake at 1: 2 with mol ratio, at pH=3-7,90-100 ℃ of following condensation reaction 1-3 hour, use the pH=6-6.5 of weak base conditioned reaction system then, and add sodium-chlor and saltout, can obtain temperature dyeing reactive dyestuffs in the said high colour-fast rate.
3. synthetic method as claimed in claim 2, the pH value when it is characterized in that condensation reaction is 4.5-6.
CN 96116228 1996-01-25 1996-01-25 Reactive dye for medium temp. dying with high colour fixation rate and method for synthesizing same Expired - Fee Related CN1059688C (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101007909B (en) * 2007-01-19 2010-05-19 武汉海图特先导材料有限公司 Macromolecule dye and its preparation and purification method, ink-jet ink using the dye

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CN106479223B (en) * 2016-10-12 2018-01-02 上海雅运纺织化工股份有限公司 Yellow active dye composition and its tint applications and method on fiber
CN109021614B (en) * 2018-08-30 2021-03-19 东华大学 Phthalocyanine azo-based double-chromophore reactive dye with high fixation rate and preparation method and application thereof
CN112300601B (en) * 2020-10-26 2022-02-15 苏州澳缘盛新材料科技有限公司 Preparation method of active dye red jade
CN112409819B (en) * 2020-10-26 2022-02-15 苏州澳缘盛新材料科技有限公司 Reactive dye red jade and application thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101007909B (en) * 2007-01-19 2010-05-19 武汉海图特先导材料有限公司 Macromolecule dye and its preparation and purification method, ink-jet ink using the dye

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