Organic compounds -- part of the class 532-570 series – Organic compounds – Azo
Reexamination Certificate
2000-11-20
2001-12-04
Powers, Fiona T. (Department: 1626)
Organic compounds -- part of the class 532-570 series
Organic compounds
Azo
C534S642000
Reexamination Certificate
active
06326474
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a reactive black dye containing acetoxyethyl sulfone moiety and more particularly, to the reactive black dye containing acetoxyethyl sulfone moiety of the following formula 1, which is characterized by lessening the loss of dyes in filtering process owing to the low solubility by introducing the aminophenyl-&bgr;-acetoxyethyl sulfone moiety, saving the cost for waste water treatment by using a small amount of salt in salting-out process and furthermore obtaining bright color with high dyeing yield and good substantivity:
wherein M is an alkaline metal atom.
2. Description of the Related Art
Conventionally, salting-out method has been adapted in order to isolate dyes from reaction mixture after synthesizing the reactive dyes. However, if aminophenyl-&bgr;-sulphatoethylsulfone is used as an intermediate in the course of manufacturing vinylsulfone-based reactive dyes, spray-dry method is adapted or large amount of salts is used because high water-solubility of dyes hinder the salting out. The isolation of dyes by spray-drying or by using large amount of salts may cause environmental pollution with waste water containing a good deal dyes and salts and eventually require much expenses on sewage treatment.
Especially, reactive black aminophenyl-&bgr;-sulphatoethylsulfone group has problems such as putting a reddish hue and lowering its substantivity because of high water-solubility.
Recently, in some developed countries such as European countries and U. S. A., there is restriction on salt concentration in dye waterwaste, thus continuous studies have been conducted in order to obtain low-salt dye and succeeded in marketing. In addition, the liquid dyes are used more favorably because they can be exactly measured and from which the automatization of dyeing process and the promotion of worker's health can be achieved. Therefore, the highly concentrated dyes by removal of salts are required for the manufacture of the stable liquid dyes.
Therefore, in comparison with dyes synthesized with aminophenyl-&bgr;-sulphatoethylsulfone group, salting-out is generally easier in the dyes synthesized with aminophenyl-&bgr;-acetoxyethylsulfone group of following formula 2, which has relatively low water solubility:
In synthesizing process of dyes with using aminophenyl-&bgr;-acetoxyethylsulfone group of the above formula 2, it is possible to lower the concentration of salt in water waste because only a small amount of salt is used in salting-out process than the conventional dyes. Also, it is cost-effective in sewage treatment because only a small amount of dyes is lost during the filtering owing to low solubility of dyes. Furthermore, thus prepared dyes has a high purity containing a small amount of salt and be able to lower the concentration of salt and make it easier desalting process in manufacturing liquid dyes.
The composition of the above formula 2 is already known and its manufacturing method is also disclosed in various documents. Among the method, one preparation method of 4-aminophenyl-&bgr;-acetoxyethylsulfone is expressed in the following Scheme1(Japanese unexamined publication Sho 81-22354; German Patent No 2 929 107):
According to the above Scheme1, 4acetaminophenyl-&bgr;-hydroxyethylsulfone and 98% of sulfuric acid is reacted to get a mixture of 70% of above formula 2 and 30% of above formula 3, and it is reported that the dyes synthesized with the mixture shows good dyeing properties. However, it has a problem that the substantivity is lowered because of high water-solubility due to the existence of 4-aminophenyl-&bgr;-sulphatoethylsulfone.
But no report has been made on synthesizing reactive black dyes introducing aminophenyl-&bgr;-acetoxyethylsulfone group of the above formula 2.
SUMMARY OF THE INVENTION
As a result of continuous studies in order to prepare reactive black dyes of high yield rate and high purity, the inventors completed this invention by synthesizing a reactive black dye introducing aminophenyl-&bgr;-ethoxyethylsulfone as a reactant.
Therefore, the object of this invention is to provide a reactive black dye of high brilliance, low degree of water-solubility and fixation, having acetoxyethylsulfone group, which decrease the amount of pollutant in process for manufacturing dye.
DETAILED DESCRIPTION OF THE INVENTION
This invention is characterized by a reactive black dye which is combined with compounds having acetoxyethylsulfone group of the following formula 1:
wherein M is an alkaline metal atom.
This invention is described in more detail as follows:
The reactive black dyes having acetoxyethylsulfone group of the above formula 1 according to this invention may be prepared in various synthesizing methods according to the kind of starting material used. For example, the following Scheme2 shows the preparing method of a reactive black dye with using aminophenyl-&bgr;-acetoxyethylsulfone as a starting material and the following Scheme3 shows another method with using aminophenyl-&bgr;-hydroxyethylsulfone as a staring material.
According to the following Scheme2, the reactive black dye is prepared by (a) diazotizing aminophenyl-&bgr;-acetoxyethylsulfone compound; (b) neutralizing 1-naphtol-8-amino-3,6-disulfonic acid compound with acid group; and (c) mixing two reaction solutions prepared in the manners as defined in (a) and (b) at temperature 0-5° C. and stirring the mixture with adjusting the pH below 7 through adding acid.
wherein M is an alkaline metal atom.
Hereunder, the preparation method according to the above Scheme2 is described more in detail.
Aminophenyl-&bgr;-acetoxyethylsulfone of formula 2 is diazotized. The diazotization method adapted in this invention is conventional one, which means that after dispersing aminophenyl-&bgr;-acetoxyethylsulfone in water at 0-5° C., the diazotzation reaction is carried with adding conc. hydrochloric acid and NaNO
2
.
And through neutralizing 1-naphthol-8-amino-3,6-disulfonic acid with using base in another reaction vessel, sulfonic acid group (—SO
3
H) of 1-naphthol-8-amino-3,6-disulfonic acid is transformed into sulfonic acid metal salt (—SO
3
M). The bases conventionally used in this reaction are alkaline metal hydroxide and alkaline metal carbonate salt and preferably NaOH, LiOH, Na
2
CO
3
and Li
2
CO
3
are used. The amount of base is determined by equivalent rate to the amount of 1-naphthol-8-amino-3,6-disulfonic acid.
After the reaction, the neutralized solution of 1-naphthol-8-amino-3,6-disulfonic acid is cooled down below 5° C. with ice, which is to carry out the coupling reaction with diazo compound at 0-5° C.
After mixing the above diazo compound and the neutralized solution of 1-naphthol-8-amino-3,6-disulfonic acid and adding base, the reaction solution is stirred at below pH 7 at 0-5° C. and resulted in reactive black dye of above formula 1. The amount of diazo compound is preferable 2-3 equivalent weight rate to 1-naphthol-8-amino-3,6-disulfonic acid. If the amount get out of the scope, side reaction may be occurred. If the pH of reaction solution exceeds 7, there is a problem in that the reaction group is hydrolyzed. If the reaction temperature becomes below 0° C., the reaction is not occurred satisfactorily and in the case of exceeding 5° C., side reaction may be occurred.
Aminophenyl-&bgr;-acetoxyethylsulfone of the above formula 2, which is used as a starting material in the above Scheme2 is prepared by reacting acetaminophenyl-&bgr;-hydroxyethylsulfone with acetic acid solution containing hydrochloric acid.
With the preparation method according to the above Scheme2, wherein aminophenyl-&bgr;-acetoxyethylsulfone compound of the above formula 2 is used as a starting material, bright colored and high purity dyes can be synthesized which cannot be acquired with aminophenyl-&bgr;-sulfatoethylsulfone.
Particularly, aminophenyl-&bgr;-acetoxyethylsulfone of formula 2 has no sulfonic acid group (—SO
3
H), which existed in aminophenyl-&bgr;-sulfatoethylsulfone of formula 3, so that the amount of alkali used in neutralization
Kang Myeong Nyeo
Kim Tae Kyung
Oh Sea Wha
Shin Seung Rim
Yun Sung Nyung
Finnegan Henderson Farabow Garrett & Dunner L.L.P.
Korea Research Institute of Chemical Technology
Powers Fiona T.
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