CA1112003A - Disazo urea dyestuff solutions - Google Patents
Disazo urea dyestuff solutionsInfo
- Publication number
- CA1112003A CA1112003A CA303,730A CA303730A CA1112003A CA 1112003 A CA1112003 A CA 1112003A CA 303730 A CA303730 A CA 303730A CA 1112003 A CA1112003 A CA 1112003A
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- Prior art keywords
- group
- formula
- methyl
- hydroxy
- stable concentrated
- Prior art date
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Classifications
-
- 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
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0072—Preparations with anionic dyes or reactive dyes
- C09B67/0073—Preparations of acid or reactive dyes in liquid form
-
- 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
- C09B43/00—Preparation of azo dyes from other azo compounds
- C09B43/12—Preparation of azo dyes from other azo compounds by acylation of amino groups
- C09B43/136—Preparation of azo dyes from other azo compounds by acylation of amino groups with polyfunctional acylating agents
- C09B43/14—Preparation of azo dyes from other azo compounds by acylation of amino groups with polyfunctional acylating agents with phosgene or thiophosgene
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Coloring (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Disazo Urea Dyestuff Solutions Abstract of the Disclosure A stable concentrated solution of an azo dyestuff is prepared by forming a tertiary alkanolammonium salt of an aminoazo compound of formula I, alone or in admixture with an aminoazo compound of formula II:
formula I formula II
formula I formula II
Description
Description of the prior art It is known to manufacture highly concentrated liquid commerical forms of dyestuffs by dissolving the dyestuff powders or pastes, in suitable aqueous, organic or organic-aqueous media, whereby highly concentrated liquid dyestuff preparations are produced, which, as regards handling and use,offer advanage6 in several respects over the dry dyestuff preparations.
Dry dye powders are troublesome to manufacture and use in the mills for dyeing paper. Drying, grinding, dust-treatment, and standardization operat-ions are required in the manufacture of the dye powders. In addition to dusting problems, the cold water beater dyeing strength of the dye powders on paper prepared from the dyed pulp is generally low.
Moreover, the slow rate at which dye powders dissolve in cold water is a particular disadvantage, especially during winter months when the temperature of water used in paper dyeing operations may approach the freezing point. This lack of solubility also makes it difficult to use such dyes in continuous systems where pumping and metering of uniform dye solutions or suspensions is necessary for .-?
efficien~ operation.
The manufacture of concentrated liquid dyestuff preparations is, however, frequently associated with difficulties, since the dyestuffs used as starting products have in most cases been obtained by salting-out and therefore contain a considerable proportion of salts, which at times are disadvantageous when manufacturing the liquid preparations, and the presence of which can have an adverse influence on the stability of such solutions.
The prior art, as exemplified by United States Patent 3,621,008 has manufactured soluble bis-urea-dyestuffs by phosgenating in aqueous solution the Na , K , Li or NH4 salt of a sulfo- or carboxyaryl-azoaryl amine where at least 50 atom percent of the cation is Li orNH4 . By the practice of the instant invention, it is possible to obtain not only dyestuffs thatare more soluble but also form stable solutions having a higher concentration of dyestuff than can be obtained by the prior art practice.
The use of a lithium base as claimed in order to maintain the desired pH value during phosgenation is very important and much superior to the use of an alkanolamine for pH-control throughout the phosgenation reaction because a rather large precipitate of alkanol-a~monium chloride forms in the latter case, which then requires -excessive dilution to dissolve the precipitate, or a major filtration operation to obtain concentrated solution.
One aspect of the present invention provides a stable concentrated dyestuff solution, containing, on a weight basis, a) about 10 to about 50 % of a dyestuff of the formula E-A-N=N-B-NH-C-NH-B'-N=N-A'-E' where E is S03H;
E' is S03H or COOH; and A, A', B and B' are each independently a naphthylene or phenyl-ene group, unsubstituted except by E and E' or further substituted by one or two groups, one of which is selected from the group con-sisting of hydroxy, nitro, cyano, trifluoromethyl, carboxy and S03N, where M is K, Na, Li or H and/or one or two is selected from the group consisting of lower alkyl, lower alkoxy, hydroxylower-alkyl, hydroxyloweralkoxy and halogen, (b) about 20 to about 90 % water, (c) about 0.1 to about 1.0 % Li ~d) less than about 1.5 % Na or K and ~e) about 3 to about 15 % of an alkanolamine of the formula .~ ~
' x-~-z where X, Y and Z are each independently loweralkyl substituted with at least one hydroxy group, loweralkoxy-loweralkyl substituted with at least one hydroxy group, or Cl-C4 alkyl, provided that no more than two of X, Y and Z are Cl-C4 alkyl.
Another aspect of the invention provides a process of making a stable concentrated dyestuff solution, comprising the step of re-acting phosgene with an aqueous solution of an alkanolamine salt of an aminoazo compound of the formula E-A-N-N-B-NH2, alone or mixed with no more than 50 mole ~ of an aminoazo compound of the formula E'-A'-N=N-B'-NH2, at a temperature of 35C to 60C, while maintain-ing the pH of the reaction solution at a value in the range of 5.0 to 8.5 with a lithium base alone or in combination with no more .;
than 35 % of triethanolamine, N-methyldiethanolamine or N,N-dimethyl-ethanolamine; wherein E is S03H;
; E' is S03H or COOH; and : ~ A, A', B and B' are each independently a naphthylene or phenylene group, unsubstituted except by E and E' or further sub-stituted by one or two groups, one of which is selected from the group consisting of hydroxy, nitro, cyano, trifluoromethyl, carboxy ~ ; and S03M, where M is K, Na,~Li or H and/or one or two is selectedr ` from the group consisting of lower alkyl, lower alkoxy, hydroxy-loweralkyl, hydroxyloweralkoxy and halogen, and wherein the alkanolamine is of the formula '. Y
., X-~-Z
where X, Y and Z are each independently loweralkyl substituted with at least one hydroxy group~ loweralkoxy-loweralkyl substituted with at least one hydroxy group, or Cl-C4alkyl, provided that no more than :` ~
:
two of X, Y and Z are Cl-C4 alkyl-The above-described phosgenation of the selected aminoazo compounds produces, in solution, disazo urea dyes of the formula O
E-A-N=N-B-NH-C-NH-B'-N-N-A'-E' wherein A, A', B, B', E and E' have the meanings set out above. The phosgenation reaction can be carried out on a single aminoazo sulfonic acid compound, or a mixture of am~inoazo sulfonic acid compounds, or a mixture of one or more aminoazo sulfonic acid compounds with one or -more aminoazo carboxylic acid compounds, provided in the latter case that at least 50 mole percent of the mixture is an aminoazo sulfonic acid compound or mixture of aminoazo sulfonic acid compounds. One skilled in the art will realize that the above structural representation of the disazo urea dyes is actually descriptive of the - average result of the phosgenation reaction. That is, when the aminoazo compound starting materials are used as a mixture (where A and A' and/
or B and B' are not identical or where a mixture of sulfonic acid and carboxylic acid dyes i8 chosen), the final product, if produced by ~ random combination, would contain some of each kind of symmetrical i~ disazourea dye as well as the unsymmetrical structure. Therefore, in addition to depicting one of the final product species present after --~ phosgenation, the above structure also represents the average i composition or the summed contributions of each of the possible - species, where mixed starting materials are used.
~
It will be appreciated from the above discussion that A and A' can be the same or different, and B and B' can be the same or different. In the discussion below of preferred A and B moieties, occurring in the starting material dyes, it should be appreciated that preferences for A and B in the starting materials also apply to A' and B' in the final product.
: .
: ~i .
It is preferred that B is phenylene, either unsubstituted or substituted with one or two substituents selected from the group consisting of methyl, methoxy and chlorine; and that A i9 phenylene or naphthylene, particularly where the substituted A is selected from the group consisting of sulfophenyl, carboxyphenyl, mono- or di-sulfonaphthyl and carboxynaphthyl, either not further substituted or substituted with one or two substituents selected from the group consisting of methyl, methoxy, ethoxy, hydroxyethyl, hydroxyethoxy and chlorine and/or one substituent selected from the group consisting of hydroxy and S03M. Especially preferred substituted A
radicals are the following: .
HO
N035 ~ _ ~_ ~
The aminoazo compounds can be prepared by well-known prior art methods,for example, by diazotizing an appropriate sulfo- and/or carboxyaryl amine, and then coupling the diazQnium compound to a second appropriate arylamine, of the benzene or naphthalene series such as an aniline, toluidine, or cresidine as such or in the form of an N-methanesulfonic acid, in which case the coupling is followed by a saponification step to obtain the aminoazo compound.
The aminoazo compound may be isolated in its free acid form after preparation. If the aminoazo compound is available as a salt, it can be converted to the free acid form by acidification in water with a strong acid such as hydrochloric acid or sulfuric acid. The precipitated acid form is filtered off and washed, as needed, to reduce further the amount of undesirable cations, e.g. with 0.1 N
hydrochloric acid containing O to 5 % sodium chloride.
~L
The production of the concentrated dyestuff solutions is for example initiated by dissolving the aforedescribed aqueous acid aminoazo compound filter cake in a sufficient amount of a liquid alkanolamine, or in a concentrated aqueous solution of such, so as to obtain a neutral or slightly alkaline solution at 20 to 50 C, which thencontains the alkanolammonium salt of the aminoazo compound.
As tertiary amines which can be used to neutralize the acid amino-azo compounds according to the invention, there are the amines of the formula Y
X-N-Z
whereby at least one of X, Y and Z is hydroxyloweralkyl or hydroxyloweralkoxyloweralkyl, optionally substituted with additional hydroxy groups, and containing from two to ~: ~ix carbon atoms, as for example the following radicals:
"
CH2CH20H, CH2CH2CH20H, CH2CROHCH3, CH2CHOHCH20H, CH2(CHOH)4CH20H, CH2-C(CH20H)3, CH2CHOHCH20CH2CH20H, CH2CH20CH2CH20H~
CH2CH20CH2CH20CH2CH20H;
and whereby up to two of X, Y and Z can also be (Cl 4~a}kyl, ~ especially methyl.
-Examples of such amines are:
CH3-N(CH2CHOHCH3)2, CH3-N(CH2CHOHCH20H)2 3-N(CH2CH20H)-CH2(CHOH~4CH20H' CH3-N(CH2CH20CH2CH2H)2' CH3-N (CH2CH20H) -CH2CH20CH2CH20CH2CH20H;
(CH3)2N-CH2C~IOHCH20H~ (CH3)2N-CH2C(CH20H)3, (CH3)2N-CH2(CHOH)4CH20H~
(CH3)2N-CH2CHOHCH20CH2CH20H, (CH3)2N-CH2CH20CH2CH20H, 3 2 3 2 H20H, (c2H5)2N-cH2cH2ocH2cH2ocH2cH2oH;
~r (HOCH CH2)2N-CH2CH2CH2H' (HCH2cH2)2N CH2 2 2 2 H0CH2CH2-N(CH2CHOHCH3)2, H0CH2CH2-N(CH2CH20CH2CH20H)2.
N(CH2CH2CH20H)3, NtCH2CH20CH2CH20H)3. N(CH2CHOHCH20H)3-Preferred tertiary alkanolamines used to neutralize the acid aminoazo compounds before phosgenation are:
Triethanolamine, N(CH2CH20H)3; 2-N,N-Dimethylaminoethanol, .-(CH3)2N-CH2CH20H; and N-methyl-diethanolamine, CH3-N(CH2CH20H)2.
The phosgenation reaction of this invention is carried out by introducing phosgene into an aqueous alkanolammonium salt solution of an appropriate aminoazo compound or a mixture of same, for example, by bubbling phosgene gas into the reaction vessel beneath the surface of the aqueous solution.
As soon as phosgene is added, the pH decreases due to the liberation of hydrogen chloride. During the reaction, the pH of the reaction mixture is maintained at 5.0 to 8.5 with a lithium base such as lithium bicarbonate, lithium carbonate, or preferably lithium hydroxide. The preferred pH is 6.5 - 7.8. At a pH less than 4.0 the reaction rate is undesirably slow and it becomes more difficult to maintain a solution or fine suspension of reactants and product. At a pH above 7.8 the competing hydrolysis of phosgene is favored, thus resulting in excessive 1088 of this reactant. The preferred base is lithium hydroxide. Lithium carbonate is re difficult to add since its low water solubility precludes use of a concentrated aqueous solution. Lithium bicarbonate is less basic and, therefore, is more costly to employ. Up to 35 % of the chosen lithium base can optionally be replaced with the equivalent of a suitable tertiary alkanolamine, particularly triethanolamine, N-methyl-diethanolamine, or 2-N,N-dimethylaminoethanol, in order to maintain the desired pH value during the introduction of phosgene.
The reaction temperature should be such that preferably a solution or a~ least a very fluid finely divided slurry is maintained throughout the reaction. The temperature selected will depend, to a certain extent, on the volume of water present, and the latter will depend, to a certain extent, on the dye concentration desired in the reaction product since the present invention makes possible the direct use of the liquid reaction product. The preferred temperature is 35-60C
since at this temperature an excellent combination of reaction rate and solubility can be achieved. Moreover, at this temperature the reaction can be carried out at atmospheric pressure, thus simplifying equipment requirements.
Theoretically, two moles of appropriate aminoazo compound are required for each mole of phosgene. Since some hydrolysis of phosgene is unavoidable, an excess of the stoichiometric amount of this reactant must be employed. Since it is difficult to predict the amount of phosgene which will be lost via hydrolysis, it is preferred to determine the progress of the reaction by removing, from time to time, a sample of the re~ction mixture and either acidifying it to observe the color change, which is tifferent with the azoamine and the phosgenated product, or eventually determining the disappearance, or near-disappearance, of original aminoazo compound(s) by a chromatographic procedure.
When the phosgenation reaction is completed, the reaction mixture is cooled and the pH is adjusted, usually to 7.0 - 8Ø The liquid reaction product then may be sampled for standardization, diluted with water or concentrated, if necessary, to achieve the desired dye strength, and packaged for direct sale and use. The process of the present invention does not preclude isolation of the dye product and the use of the resultant dye powder in a manner analogous to similar prior art dyes. All of the advantages of the present invention relative to improved preparation,higher solubility of the dyes and g the like, accrue to dye powders prepared by means of this invention.
However, since the present process provides a concentrated liquid product, economics often favors the use of the liquid products directly. By the process of the present invention stable aqueous ;
solutions containing about 10 to about 50 weight percent active dye ingredient can be prepared. Moreover, the process of this present invention permits the introduction of additives, for example urea, organic solvents, or dispersing agents directly to the phosgenation reaction mixture.
. .
Auxiliary solubilizing agents, which can optionally be added include:
the amides of inorganic or organic acids, preferably carboxylic acid amides, e.g. those of monobasic or dibasic carboxylic acids, such as the amides of carboxylic acids containing up to 8 carbon atoms, e.g.
Dry dye powders are troublesome to manufacture and use in the mills for dyeing paper. Drying, grinding, dust-treatment, and standardization operat-ions are required in the manufacture of the dye powders. In addition to dusting problems, the cold water beater dyeing strength of the dye powders on paper prepared from the dyed pulp is generally low.
Moreover, the slow rate at which dye powders dissolve in cold water is a particular disadvantage, especially during winter months when the temperature of water used in paper dyeing operations may approach the freezing point. This lack of solubility also makes it difficult to use such dyes in continuous systems where pumping and metering of uniform dye solutions or suspensions is necessary for .-?
efficien~ operation.
The manufacture of concentrated liquid dyestuff preparations is, however, frequently associated with difficulties, since the dyestuffs used as starting products have in most cases been obtained by salting-out and therefore contain a considerable proportion of salts, which at times are disadvantageous when manufacturing the liquid preparations, and the presence of which can have an adverse influence on the stability of such solutions.
The prior art, as exemplified by United States Patent 3,621,008 has manufactured soluble bis-urea-dyestuffs by phosgenating in aqueous solution the Na , K , Li or NH4 salt of a sulfo- or carboxyaryl-azoaryl amine where at least 50 atom percent of the cation is Li orNH4 . By the practice of the instant invention, it is possible to obtain not only dyestuffs thatare more soluble but also form stable solutions having a higher concentration of dyestuff than can be obtained by the prior art practice.
The use of a lithium base as claimed in order to maintain the desired pH value during phosgenation is very important and much superior to the use of an alkanolamine for pH-control throughout the phosgenation reaction because a rather large precipitate of alkanol-a~monium chloride forms in the latter case, which then requires -excessive dilution to dissolve the precipitate, or a major filtration operation to obtain concentrated solution.
One aspect of the present invention provides a stable concentrated dyestuff solution, containing, on a weight basis, a) about 10 to about 50 % of a dyestuff of the formula E-A-N=N-B-NH-C-NH-B'-N=N-A'-E' where E is S03H;
E' is S03H or COOH; and A, A', B and B' are each independently a naphthylene or phenyl-ene group, unsubstituted except by E and E' or further substituted by one or two groups, one of which is selected from the group con-sisting of hydroxy, nitro, cyano, trifluoromethyl, carboxy and S03N, where M is K, Na, Li or H and/or one or two is selected from the group consisting of lower alkyl, lower alkoxy, hydroxylower-alkyl, hydroxyloweralkoxy and halogen, (b) about 20 to about 90 % water, (c) about 0.1 to about 1.0 % Li ~d) less than about 1.5 % Na or K and ~e) about 3 to about 15 % of an alkanolamine of the formula .~ ~
' x-~-z where X, Y and Z are each independently loweralkyl substituted with at least one hydroxy group, loweralkoxy-loweralkyl substituted with at least one hydroxy group, or Cl-C4 alkyl, provided that no more than two of X, Y and Z are Cl-C4 alkyl.
Another aspect of the invention provides a process of making a stable concentrated dyestuff solution, comprising the step of re-acting phosgene with an aqueous solution of an alkanolamine salt of an aminoazo compound of the formula E-A-N-N-B-NH2, alone or mixed with no more than 50 mole ~ of an aminoazo compound of the formula E'-A'-N=N-B'-NH2, at a temperature of 35C to 60C, while maintain-ing the pH of the reaction solution at a value in the range of 5.0 to 8.5 with a lithium base alone or in combination with no more .;
than 35 % of triethanolamine, N-methyldiethanolamine or N,N-dimethyl-ethanolamine; wherein E is S03H;
; E' is S03H or COOH; and : ~ A, A', B and B' are each independently a naphthylene or phenylene group, unsubstituted except by E and E' or further sub-stituted by one or two groups, one of which is selected from the group consisting of hydroxy, nitro, cyano, trifluoromethyl, carboxy ~ ; and S03M, where M is K, Na,~Li or H and/or one or two is selectedr ` from the group consisting of lower alkyl, lower alkoxy, hydroxy-loweralkyl, hydroxyloweralkoxy and halogen, and wherein the alkanolamine is of the formula '. Y
., X-~-Z
where X, Y and Z are each independently loweralkyl substituted with at least one hydroxy group~ loweralkoxy-loweralkyl substituted with at least one hydroxy group, or Cl-C4alkyl, provided that no more than :` ~
:
two of X, Y and Z are Cl-C4 alkyl-The above-described phosgenation of the selected aminoazo compounds produces, in solution, disazo urea dyes of the formula O
E-A-N=N-B-NH-C-NH-B'-N-N-A'-E' wherein A, A', B, B', E and E' have the meanings set out above. The phosgenation reaction can be carried out on a single aminoazo sulfonic acid compound, or a mixture of am~inoazo sulfonic acid compounds, or a mixture of one or more aminoazo sulfonic acid compounds with one or -more aminoazo carboxylic acid compounds, provided in the latter case that at least 50 mole percent of the mixture is an aminoazo sulfonic acid compound or mixture of aminoazo sulfonic acid compounds. One skilled in the art will realize that the above structural representation of the disazo urea dyes is actually descriptive of the - average result of the phosgenation reaction. That is, when the aminoazo compound starting materials are used as a mixture (where A and A' and/
or B and B' are not identical or where a mixture of sulfonic acid and carboxylic acid dyes i8 chosen), the final product, if produced by ~ random combination, would contain some of each kind of symmetrical i~ disazourea dye as well as the unsymmetrical structure. Therefore, in addition to depicting one of the final product species present after --~ phosgenation, the above structure also represents the average i composition or the summed contributions of each of the possible - species, where mixed starting materials are used.
~
It will be appreciated from the above discussion that A and A' can be the same or different, and B and B' can be the same or different. In the discussion below of preferred A and B moieties, occurring in the starting material dyes, it should be appreciated that preferences for A and B in the starting materials also apply to A' and B' in the final product.
: .
: ~i .
It is preferred that B is phenylene, either unsubstituted or substituted with one or two substituents selected from the group consisting of methyl, methoxy and chlorine; and that A i9 phenylene or naphthylene, particularly where the substituted A is selected from the group consisting of sulfophenyl, carboxyphenyl, mono- or di-sulfonaphthyl and carboxynaphthyl, either not further substituted or substituted with one or two substituents selected from the group consisting of methyl, methoxy, ethoxy, hydroxyethyl, hydroxyethoxy and chlorine and/or one substituent selected from the group consisting of hydroxy and S03M. Especially preferred substituted A
radicals are the following: .
HO
N035 ~ _ ~_ ~
The aminoazo compounds can be prepared by well-known prior art methods,for example, by diazotizing an appropriate sulfo- and/or carboxyaryl amine, and then coupling the diazQnium compound to a second appropriate arylamine, of the benzene or naphthalene series such as an aniline, toluidine, or cresidine as such or in the form of an N-methanesulfonic acid, in which case the coupling is followed by a saponification step to obtain the aminoazo compound.
The aminoazo compound may be isolated in its free acid form after preparation. If the aminoazo compound is available as a salt, it can be converted to the free acid form by acidification in water with a strong acid such as hydrochloric acid or sulfuric acid. The precipitated acid form is filtered off and washed, as needed, to reduce further the amount of undesirable cations, e.g. with 0.1 N
hydrochloric acid containing O to 5 % sodium chloride.
~L
The production of the concentrated dyestuff solutions is for example initiated by dissolving the aforedescribed aqueous acid aminoazo compound filter cake in a sufficient amount of a liquid alkanolamine, or in a concentrated aqueous solution of such, so as to obtain a neutral or slightly alkaline solution at 20 to 50 C, which thencontains the alkanolammonium salt of the aminoazo compound.
As tertiary amines which can be used to neutralize the acid amino-azo compounds according to the invention, there are the amines of the formula Y
X-N-Z
whereby at least one of X, Y and Z is hydroxyloweralkyl or hydroxyloweralkoxyloweralkyl, optionally substituted with additional hydroxy groups, and containing from two to ~: ~ix carbon atoms, as for example the following radicals:
"
CH2CH20H, CH2CH2CH20H, CH2CROHCH3, CH2CHOHCH20H, CH2(CHOH)4CH20H, CH2-C(CH20H)3, CH2CHOHCH20CH2CH20H, CH2CH20CH2CH20H~
CH2CH20CH2CH20CH2CH20H;
and whereby up to two of X, Y and Z can also be (Cl 4~a}kyl, ~ especially methyl.
-Examples of such amines are:
CH3-N(CH2CHOHCH3)2, CH3-N(CH2CHOHCH20H)2 3-N(CH2CH20H)-CH2(CHOH~4CH20H' CH3-N(CH2CH20CH2CH2H)2' CH3-N (CH2CH20H) -CH2CH20CH2CH20CH2CH20H;
(CH3)2N-CH2C~IOHCH20H~ (CH3)2N-CH2C(CH20H)3, (CH3)2N-CH2(CHOH)4CH20H~
(CH3)2N-CH2CHOHCH20CH2CH20H, (CH3)2N-CH2CH20CH2CH20H, 3 2 3 2 H20H, (c2H5)2N-cH2cH2ocH2cH2ocH2cH2oH;
~r (HOCH CH2)2N-CH2CH2CH2H' (HCH2cH2)2N CH2 2 2 2 H0CH2CH2-N(CH2CHOHCH3)2, H0CH2CH2-N(CH2CH20CH2CH20H)2.
N(CH2CH2CH20H)3, NtCH2CH20CH2CH20H)3. N(CH2CHOHCH20H)3-Preferred tertiary alkanolamines used to neutralize the acid aminoazo compounds before phosgenation are:
Triethanolamine, N(CH2CH20H)3; 2-N,N-Dimethylaminoethanol, .-(CH3)2N-CH2CH20H; and N-methyl-diethanolamine, CH3-N(CH2CH20H)2.
The phosgenation reaction of this invention is carried out by introducing phosgene into an aqueous alkanolammonium salt solution of an appropriate aminoazo compound or a mixture of same, for example, by bubbling phosgene gas into the reaction vessel beneath the surface of the aqueous solution.
As soon as phosgene is added, the pH decreases due to the liberation of hydrogen chloride. During the reaction, the pH of the reaction mixture is maintained at 5.0 to 8.5 with a lithium base such as lithium bicarbonate, lithium carbonate, or preferably lithium hydroxide. The preferred pH is 6.5 - 7.8. At a pH less than 4.0 the reaction rate is undesirably slow and it becomes more difficult to maintain a solution or fine suspension of reactants and product. At a pH above 7.8 the competing hydrolysis of phosgene is favored, thus resulting in excessive 1088 of this reactant. The preferred base is lithium hydroxide. Lithium carbonate is re difficult to add since its low water solubility precludes use of a concentrated aqueous solution. Lithium bicarbonate is less basic and, therefore, is more costly to employ. Up to 35 % of the chosen lithium base can optionally be replaced with the equivalent of a suitable tertiary alkanolamine, particularly triethanolamine, N-methyl-diethanolamine, or 2-N,N-dimethylaminoethanol, in order to maintain the desired pH value during the introduction of phosgene.
The reaction temperature should be such that preferably a solution or a~ least a very fluid finely divided slurry is maintained throughout the reaction. The temperature selected will depend, to a certain extent, on the volume of water present, and the latter will depend, to a certain extent, on the dye concentration desired in the reaction product since the present invention makes possible the direct use of the liquid reaction product. The preferred temperature is 35-60C
since at this temperature an excellent combination of reaction rate and solubility can be achieved. Moreover, at this temperature the reaction can be carried out at atmospheric pressure, thus simplifying equipment requirements.
Theoretically, two moles of appropriate aminoazo compound are required for each mole of phosgene. Since some hydrolysis of phosgene is unavoidable, an excess of the stoichiometric amount of this reactant must be employed. Since it is difficult to predict the amount of phosgene which will be lost via hydrolysis, it is preferred to determine the progress of the reaction by removing, from time to time, a sample of the re~ction mixture and either acidifying it to observe the color change, which is tifferent with the azoamine and the phosgenated product, or eventually determining the disappearance, or near-disappearance, of original aminoazo compound(s) by a chromatographic procedure.
When the phosgenation reaction is completed, the reaction mixture is cooled and the pH is adjusted, usually to 7.0 - 8Ø The liquid reaction product then may be sampled for standardization, diluted with water or concentrated, if necessary, to achieve the desired dye strength, and packaged for direct sale and use. The process of the present invention does not preclude isolation of the dye product and the use of the resultant dye powder in a manner analogous to similar prior art dyes. All of the advantages of the present invention relative to improved preparation,higher solubility of the dyes and g the like, accrue to dye powders prepared by means of this invention.
However, since the present process provides a concentrated liquid product, economics often favors the use of the liquid products directly. By the process of the present invention stable aqueous ;
solutions containing about 10 to about 50 weight percent active dye ingredient can be prepared. Moreover, the process of this present invention permits the introduction of additives, for example urea, organic solvents, or dispersing agents directly to the phosgenation reaction mixture.
. .
Auxiliary solubilizing agents, which can optionally be added include:
the amides of inorganic or organic acids, preferably carboxylic acid amides, e.g. those of monobasic or dibasic carboxylic acids, such as the amides of carboxylic acids containing up to 8 carbon atoms, e.g.
2 to 4 carbon atoms, such as acetamide, propionic acid amide, as well as malonic acid diamide. Urea and urea derivatives are partic-ularly suitable; examples besides urea itself are substituted or unsubstituted alkylurea compounds such as methyl and ethyl urea, N,N'-dimethylurea and dihydroxyloweralkyl ureas. Further guanidine and its derivatives such as methyl guanidine are suitable. Also formamides such as alkyl formamide, e.g. methyl- and dimethyl-formamide can be used as well as sulphonic acid amides or diamides.
There can also be added glycols and glycol ethers such as Cellosolve*, Carbitol*, etc.
Further auxiliary agents are, for example, antifoaming agents.
The new process is particularly valuable for the manufacture of disazo dyestuffs of the formula o E-A-N=N-B-NH-C-NH-B'-N~N-A'-E' * Trademarks wherein -A-E- and -A'-E' represent radicals of disazo components of the sulphobenzene or the mono- or di-sulphonaphthalene series and B and B' represent radicals of coupling components of the benzene series (see, for instance, Examples 3 and 4); and wherein A and A' and/or B and B' can also be identical as,for instance, described in Example 1.
Likewise, the new process is particularly valuable for the manufacture of disazo dyestuffs of the same formula wherein E-A-represents a radical of a diazo component of the sulphobenzene or the mono- or di-sulphonaphthalene series, E'-A'- represents a radical of the carboxybenzene or carboxynaphthalene series and B and B' are as above, as for instance, described in Example 2.
The highly concentrated solutions of tertiary ammonium salts of direct dyes obtained according to the process of this invention contain on a weight basis, a) 10 to 50 %, especially 18 to 40 %, of the tertiary alkanolammonium salt of a disazo urea dyestuff, as described above, b) about 20 to about 90 % of water, especially about 50 to about 80 %, c) about 1 % or less of Li but especially about 0.5 - 0.9 %, d) under about 1.5 % of Na , especially about 0.05 - 1.0 %, e) about 3 - 15 % tertiary alkanolammonium salt, calculated as free amine, especially about 3.5 - 10 %, and f) 0 to about 40 % of an auxiliary agent or a combination of auxiliary agents, especially a solubility-enhancing agent.
~1 .
The highly concentrated solutions prove stable even on prolonged standing and the dyestuff neither crystallizes out nor decomposes.
They are miscible in any ratio with water and/or water miscible organic solvents. They are particularly suitable for the manufacture of solutions for dyeing paper pulp and for dyeing textile fibers, but can also be used for other purposes.
The dyes of the present invention may be used directly in the form of a solution as prepared, or as dry powders, to dye cellulosic materials, especially paper, in the usual paper mill equipment. The following description represents a typical dyeing operation. Normally 0.1 to 3.0 parts of the dye liquid are added to an aqueous slurry of 100 parts (dry basis) of bleached sulfite pulp in 5,000 parts of water at ambient temperature (2-38C); 0.5 to 3 parts of rosin size (sodium rosinate) and 1 to 4 parts of aluminum sulfate octadecahydrate then added. The mixture is thoroughly agitated for 10 to 20 minutes and water is added as needed to give a total of 20,000 to 25,000 parts. Paper sheet is then made up in the usual manner. The dye liquids of the invention can also be used for continuous coloring of paper by constant metering of the dye liquid into the pulp slurry, or in liquid formulations for the dyeing and printing of paper and cardboard by surface application.
Example 1: 84.2 parts of 2-(4'-amino-2'-tolylazo)-naphthalene-6,8-disulfonic-acid obtained by combining diazotized 2-amino-naphthalene-6,8-disulfanic acid with m-toluidine in a known manner, e.g. in aqueous medium at 10 to 25C and a pH value adjusted to 3, and isolating the precipitated coupling product at a pH near 1 through filtration followed by washing with sufficient 0.1 normal hydrochloric acid to replace most of the salt-containing mother liquid from the filter cake, as filter cake containing about 50 %
water, are dissolved ir. 36 parts of triethanolamine and 24 parts of : ` :
water at pH 7 to 8 and 35C. Phosgene is introduced under agitation and the temperature is permitted to rise over 40C. The dropping pH value is held at 6.7 to 7.5 by the gradual addition of 4.6 normal aqueous lithium hydroxide solution until the aminoazo compound is largely used up. (It required about 25 parts of phosgene and 11 to 12 parts of LiOH in a period of about 2 hours to obtain about 360 parts of liquid).
The thin suspension is diluted with 180 parts of hot water and clarified at 70C in the presence of 3 parts of Dicalite* to remove a small amount of fine insoluble material. About 540 parts of solution are obtained which is stable in customary storage and resistant to chilling induced precipitation. It contains 27 % solids , ., including about 22 Z dyestuff alkanolamine salt.
It dyes paper fibers from cold or hot water in reddish yellow shades.
When the dilution of the thin suspension is done with 54 parts of Cellosolve (or a mixture of Cellosolve and Carbitol, totaling 54 parts) in place of the 180 parts of water and the remainder of the procedure is carried out as before, 414 parts of solution is obtained (containing about 35 ~ solids including 29 ~ dyestuff alkanolamine salt).
When the 36 parts of triethanolamine above are replaced by 27 parts of N-methyl-diethanolamine-2 or 20 parts of 2-N,N-dimethylaminoethanol, respectively, stable solutions are obtained after a final dilution with water to get 540 parts, as before. If ca. 100 parts of water are added in the beginning, a-solution is maintained throughout the reaction.
* Trademark :: :
q ?3 When urea is added to the above aqueous solutions in the amount of 4 to12 % by weight, their stability is prolonged. Additions of 6 - 12 %
triethylene glycol or 4 - 8 % "Ethomeen* C/25" (by Armour) have a similar effect.
Example 2: 61,4 parts of 4-amino-3-methoxy-azobenzene-3'-sulfonic acidand 51.4 parts of 4-hydroxy-4'-aminoazobenzene-3-carboxylic acid, as filter cakes containing 60 to 70 % water are dissolved at pH 7 to 8 in 79 parts of triethanolamine, 75 parts of Carbitol is added and a total of ca. 45 parts of phosgene is introduced under agitation at 35 to 45C while a pH range of 6.8 to 7.8 is maintained by the simultaneous addition of 4.6 normal aqueous lithium hydroxide solution (containing a total of about 40 parts of LiOH-H20) until the aminoazo compounts are largely used up. 75 parts of Carbitol are added during the phosgenation and the final suspension is dissolved completely with 140 parts of Cellosolve. 960 parts of stable solution are obtained (containing about 25 % solids and including 18 % dyestuff alkanolamine salt) which dyes paper, cotton and nylon in fast greenish yellow shades.
The aminoazo compounds used were obtained by processing the weakly alkaline filter cakes regularly available after e.g. combining diazotized metanilic acid and sodium o-anisidine-~-methanesulfonate unter known aqueous conditions, followed by hot alkaline saponification, salting and cold filtration on the one hand; and, on the other, combining diazotized p-nitroaniline and salicylic acid under known aqueous contitions, followed by retuction of the nitro group with sodium sulfide, salting, filtration and brine washing;
as follows:
Dissolve the sodium 4-amino-3-methoxy-azobenzene-3'-sulfonate in water (ca. 1:10) at 25 to 30C, acidify with conc. hydrochloric acid *Trademark .~, . ., , ~ ,. ,, -.
to about pH 1, filter the precipitated free acid form and wash with N/10 hydrochloric acid to replace most of the salt-containing mother liquor from the filter cake. Dissolve the sodium 4-hydroxy-4'-amino-benzene-3-carboxylate in water (ca. 1:20) at 60C, acidify with conc.
hydrochloric acid to about pH 1, filter the precipitated free acid form at 40C and wash liberally with N/10 hydrochloric acid.
Example 3: 61.4 parts of 4-amino-3~E~hoxy-azobenzene-3'-sulfonic acid, obtained as described in Example 2, and 84.2 parts of 2-(4'-amino-2'-tolylazo)-naphthalene-4,'8-disulfonic acid, obtained in a manner similar to that described for the starting material of Example 1, are dissolved as filter cakes at pH 7 to 8 in 76 parts of triethanolamine.
Phosgene is introduced under agitation'at 35 - 60C, while a pH
range of 6.8 to 7.8 is maintained by the simultaneous addition of 4.6 normal aqueous lithium hydroxide solution (containing a total of about 40 parts of LiOH-H2o) until the amino compounds are largely used up. About 690 parts of solution are obtained. When 11.1 parts of urea are dissolved in each 100 parts of said solution, it remains stable between 0 and 50C in customary storage and contains about 28 ~ dyestuff alkanolamine salt.
When the phosgenated solution, before dilution with urea, is spray dried, a very water soluble powder is obtained.
When the 84.2 parts of 2-(4'-amino-2'-tolylazo)-naphthalene-4,8-disulfonic acid in the above example are doubled while no 4-amino-3-methoxy-azobenzene-3'-sulfonic acid is used as starting material, and the final dilution is carried out as above or proportionately as outlined in Example 1, the corresponding dyestuff solutions are obtained.
The solutions described in this example dye paper by the customar procedures from hot or cold dye baths in fast and strong yellow shades.
... .
Example 4: 21 parts of 2-(4'-amino-2'-tolylazo)-naphthalene-6,8-disulfonic acid (obtained as described in Example 1), 20.4 parts of 2-(4'-aminophenylazo)-naphthalene-6,8-disulfonic acid and 30.7 parts of 4-amino-3-methoxy-azobenzene-3'-sulfonic acid (both obtained as described for the latter in Example 2), are dissolved, as filter cakes, in 36 parts of triethanolamino at a pH 7 to 8 and 35C.
Phosgene and lithium hydroxide are introduced as described in Example 1and Cellosolve and Carbitol - in the total amount of 25 to 35 parts per final weight of ~he dyestuff solution, and at least five parts of Cellosolve and 10 parts of Carbitol - are added gradually or in one or several portions so as to prevent serious thickening or maintain a solution until the amino compounds are largely used up. (This required not more than 30 parts of phosgene and 13 parts of LiOH. It took 2 to 2 L/2 hours.) 450 to 500 parts of a stable solution are obtained, which contains about 21 - 23 % alkanolamine dyestuff salt and dyes paper and cotton in strong yellow shades.
By following the procedures exemplified above one or more of the following compounds can be reacted to yield stable concentrated solutions of dyestuffs substantive for cellulose.
~ ~--N=N--~ ~--NH2 .=. =--S~3H OCH3 HO S--~ ~--N=N--~ ~--NH
C~
~ $1~ 3 _ _ --N=N~ --NH2 ~ S~3H CH3 :, :, ._. ._.
.=. ~.=./ 2 HOOC~
HO--~ ~--N3N--~ ~--NH2 . C~ .
HOOC~ ~OCH3 Cl--~ ~--N-N--~ ~--NH2 .,.. .~.
HOOC~
HO--~ ~--N-N--~ ~--NH2 HOOC~ ~OH
-N-N--~ ~--NH2 SO3H 3~
~ t-N-N--~ ~--NH2 SO3H CH3~
T b t N N--~ ~--NH2 ~./-\.~- =-, .: ::
:. : ~ , : SO3H
t~ il t-N=N--\ ~ NH2 HO S i~-/ \-~
SO3H ~OCH3 -N=N- -~ ~ NH2 i HO3S ~
SO3H ~OCH3 i~ t -N'N- -~ ~--NH2 ./ \.~
There can also be added glycols and glycol ethers such as Cellosolve*, Carbitol*, etc.
Further auxiliary agents are, for example, antifoaming agents.
The new process is particularly valuable for the manufacture of disazo dyestuffs of the formula o E-A-N=N-B-NH-C-NH-B'-N~N-A'-E' * Trademarks wherein -A-E- and -A'-E' represent radicals of disazo components of the sulphobenzene or the mono- or di-sulphonaphthalene series and B and B' represent radicals of coupling components of the benzene series (see, for instance, Examples 3 and 4); and wherein A and A' and/or B and B' can also be identical as,for instance, described in Example 1.
Likewise, the new process is particularly valuable for the manufacture of disazo dyestuffs of the same formula wherein E-A-represents a radical of a diazo component of the sulphobenzene or the mono- or di-sulphonaphthalene series, E'-A'- represents a radical of the carboxybenzene or carboxynaphthalene series and B and B' are as above, as for instance, described in Example 2.
The highly concentrated solutions of tertiary ammonium salts of direct dyes obtained according to the process of this invention contain on a weight basis, a) 10 to 50 %, especially 18 to 40 %, of the tertiary alkanolammonium salt of a disazo urea dyestuff, as described above, b) about 20 to about 90 % of water, especially about 50 to about 80 %, c) about 1 % or less of Li but especially about 0.5 - 0.9 %, d) under about 1.5 % of Na , especially about 0.05 - 1.0 %, e) about 3 - 15 % tertiary alkanolammonium salt, calculated as free amine, especially about 3.5 - 10 %, and f) 0 to about 40 % of an auxiliary agent or a combination of auxiliary agents, especially a solubility-enhancing agent.
~1 .
The highly concentrated solutions prove stable even on prolonged standing and the dyestuff neither crystallizes out nor decomposes.
They are miscible in any ratio with water and/or water miscible organic solvents. They are particularly suitable for the manufacture of solutions for dyeing paper pulp and for dyeing textile fibers, but can also be used for other purposes.
The dyes of the present invention may be used directly in the form of a solution as prepared, or as dry powders, to dye cellulosic materials, especially paper, in the usual paper mill equipment. The following description represents a typical dyeing operation. Normally 0.1 to 3.0 parts of the dye liquid are added to an aqueous slurry of 100 parts (dry basis) of bleached sulfite pulp in 5,000 parts of water at ambient temperature (2-38C); 0.5 to 3 parts of rosin size (sodium rosinate) and 1 to 4 parts of aluminum sulfate octadecahydrate then added. The mixture is thoroughly agitated for 10 to 20 minutes and water is added as needed to give a total of 20,000 to 25,000 parts. Paper sheet is then made up in the usual manner. The dye liquids of the invention can also be used for continuous coloring of paper by constant metering of the dye liquid into the pulp slurry, or in liquid formulations for the dyeing and printing of paper and cardboard by surface application.
Example 1: 84.2 parts of 2-(4'-amino-2'-tolylazo)-naphthalene-6,8-disulfonic-acid obtained by combining diazotized 2-amino-naphthalene-6,8-disulfanic acid with m-toluidine in a known manner, e.g. in aqueous medium at 10 to 25C and a pH value adjusted to 3, and isolating the precipitated coupling product at a pH near 1 through filtration followed by washing with sufficient 0.1 normal hydrochloric acid to replace most of the salt-containing mother liquid from the filter cake, as filter cake containing about 50 %
water, are dissolved ir. 36 parts of triethanolamine and 24 parts of : ` :
water at pH 7 to 8 and 35C. Phosgene is introduced under agitation and the temperature is permitted to rise over 40C. The dropping pH value is held at 6.7 to 7.5 by the gradual addition of 4.6 normal aqueous lithium hydroxide solution until the aminoazo compound is largely used up. (It required about 25 parts of phosgene and 11 to 12 parts of LiOH in a period of about 2 hours to obtain about 360 parts of liquid).
The thin suspension is diluted with 180 parts of hot water and clarified at 70C in the presence of 3 parts of Dicalite* to remove a small amount of fine insoluble material. About 540 parts of solution are obtained which is stable in customary storage and resistant to chilling induced precipitation. It contains 27 % solids , ., including about 22 Z dyestuff alkanolamine salt.
It dyes paper fibers from cold or hot water in reddish yellow shades.
When the dilution of the thin suspension is done with 54 parts of Cellosolve (or a mixture of Cellosolve and Carbitol, totaling 54 parts) in place of the 180 parts of water and the remainder of the procedure is carried out as before, 414 parts of solution is obtained (containing about 35 ~ solids including 29 ~ dyestuff alkanolamine salt).
When the 36 parts of triethanolamine above are replaced by 27 parts of N-methyl-diethanolamine-2 or 20 parts of 2-N,N-dimethylaminoethanol, respectively, stable solutions are obtained after a final dilution with water to get 540 parts, as before. If ca. 100 parts of water are added in the beginning, a-solution is maintained throughout the reaction.
* Trademark :: :
q ?3 When urea is added to the above aqueous solutions in the amount of 4 to12 % by weight, their stability is prolonged. Additions of 6 - 12 %
triethylene glycol or 4 - 8 % "Ethomeen* C/25" (by Armour) have a similar effect.
Example 2: 61,4 parts of 4-amino-3-methoxy-azobenzene-3'-sulfonic acidand 51.4 parts of 4-hydroxy-4'-aminoazobenzene-3-carboxylic acid, as filter cakes containing 60 to 70 % water are dissolved at pH 7 to 8 in 79 parts of triethanolamine, 75 parts of Carbitol is added and a total of ca. 45 parts of phosgene is introduced under agitation at 35 to 45C while a pH range of 6.8 to 7.8 is maintained by the simultaneous addition of 4.6 normal aqueous lithium hydroxide solution (containing a total of about 40 parts of LiOH-H20) until the aminoazo compounts are largely used up. 75 parts of Carbitol are added during the phosgenation and the final suspension is dissolved completely with 140 parts of Cellosolve. 960 parts of stable solution are obtained (containing about 25 % solids and including 18 % dyestuff alkanolamine salt) which dyes paper, cotton and nylon in fast greenish yellow shades.
The aminoazo compounds used were obtained by processing the weakly alkaline filter cakes regularly available after e.g. combining diazotized metanilic acid and sodium o-anisidine-~-methanesulfonate unter known aqueous conditions, followed by hot alkaline saponification, salting and cold filtration on the one hand; and, on the other, combining diazotized p-nitroaniline and salicylic acid under known aqueous contitions, followed by retuction of the nitro group with sodium sulfide, salting, filtration and brine washing;
as follows:
Dissolve the sodium 4-amino-3-methoxy-azobenzene-3'-sulfonate in water (ca. 1:10) at 25 to 30C, acidify with conc. hydrochloric acid *Trademark .~, . ., , ~ ,. ,, -.
to about pH 1, filter the precipitated free acid form and wash with N/10 hydrochloric acid to replace most of the salt-containing mother liquor from the filter cake. Dissolve the sodium 4-hydroxy-4'-amino-benzene-3-carboxylate in water (ca. 1:20) at 60C, acidify with conc.
hydrochloric acid to about pH 1, filter the precipitated free acid form at 40C and wash liberally with N/10 hydrochloric acid.
Example 3: 61.4 parts of 4-amino-3~E~hoxy-azobenzene-3'-sulfonic acid, obtained as described in Example 2, and 84.2 parts of 2-(4'-amino-2'-tolylazo)-naphthalene-4,'8-disulfonic acid, obtained in a manner similar to that described for the starting material of Example 1, are dissolved as filter cakes at pH 7 to 8 in 76 parts of triethanolamine.
Phosgene is introduced under agitation'at 35 - 60C, while a pH
range of 6.8 to 7.8 is maintained by the simultaneous addition of 4.6 normal aqueous lithium hydroxide solution (containing a total of about 40 parts of LiOH-H2o) until the amino compounds are largely used up. About 690 parts of solution are obtained. When 11.1 parts of urea are dissolved in each 100 parts of said solution, it remains stable between 0 and 50C in customary storage and contains about 28 ~ dyestuff alkanolamine salt.
When the phosgenated solution, before dilution with urea, is spray dried, a very water soluble powder is obtained.
When the 84.2 parts of 2-(4'-amino-2'-tolylazo)-naphthalene-4,8-disulfonic acid in the above example are doubled while no 4-amino-3-methoxy-azobenzene-3'-sulfonic acid is used as starting material, and the final dilution is carried out as above or proportionately as outlined in Example 1, the corresponding dyestuff solutions are obtained.
The solutions described in this example dye paper by the customar procedures from hot or cold dye baths in fast and strong yellow shades.
... .
Example 4: 21 parts of 2-(4'-amino-2'-tolylazo)-naphthalene-6,8-disulfonic acid (obtained as described in Example 1), 20.4 parts of 2-(4'-aminophenylazo)-naphthalene-6,8-disulfonic acid and 30.7 parts of 4-amino-3-methoxy-azobenzene-3'-sulfonic acid (both obtained as described for the latter in Example 2), are dissolved, as filter cakes, in 36 parts of triethanolamino at a pH 7 to 8 and 35C.
Phosgene and lithium hydroxide are introduced as described in Example 1and Cellosolve and Carbitol - in the total amount of 25 to 35 parts per final weight of ~he dyestuff solution, and at least five parts of Cellosolve and 10 parts of Carbitol - are added gradually or in one or several portions so as to prevent serious thickening or maintain a solution until the amino compounds are largely used up. (This required not more than 30 parts of phosgene and 13 parts of LiOH. It took 2 to 2 L/2 hours.) 450 to 500 parts of a stable solution are obtained, which contains about 21 - 23 % alkanolamine dyestuff salt and dyes paper and cotton in strong yellow shades.
By following the procedures exemplified above one or more of the following compounds can be reacted to yield stable concentrated solutions of dyestuffs substantive for cellulose.
~ ~--N=N--~ ~--NH2 .=. =--S~3H OCH3 HO S--~ ~--N=N--~ ~--NH
C~
~ $1~ 3 _ _ --N=N~ --NH2 ~ S~3H CH3 :, :, ._. ._.
.=. ~.=./ 2 HOOC~
HO--~ ~--N3N--~ ~--NH2 . C~ .
HOOC~ ~OCH3 Cl--~ ~--N-N--~ ~--NH2 .,.. .~.
HOOC~
HO--~ ~--N-N--~ ~--NH2 HOOC~ ~OH
-N-N--~ ~--NH2 SO3H 3~
~ t-N-N--~ ~--NH2 SO3H CH3~
T b t N N--~ ~--NH2 ~./-\.~- =-, .: ::
:. : ~ , : SO3H
t~ il t-N=N--\ ~ NH2 HO S i~-/ \-~
SO3H ~OCH3 -N=N- -~ ~ NH2 i HO3S ~
SO3H ~OCH3 i~ t -N'N- -~ ~--NH2 ./ \.~
3 \ ~ t-N-N--~ ~--NH2 ~./\.,~ /
~ ~--SO H
HO3S--~ ~--N=N--~ ~--NH2 SO3H ~OCH3 t~ t-N=N--\ ~ N 2 SO;H 3 . ~ ~
-- ~ ,:
:, \, / ._.
/ \--N=H~ --NH
i il ~i-N=N--~ ~--NH
HO S/ ~ O/CH3 ~SO3H
\ /
/ \--N-N--~ ~--NH
O~H3 ~ ~ N=N--~ ~--NH2 - S~;H
- ~Cl HO
HO3S--~ ~.-N-N-~ /NH2 - :. :
~L$~ 3 HO
\ ~--N=N- t~ T'N 2 3 SO;H
OH
Ho-C2H40--~ ~.-N-N-t il t HO
._ . . .
103H ~OCH3 t~ t-N=N;--~ NH
t~
t iI t N-N--~ ~--NH2 ~03E
t-NSN--~ ~--NH2 :. /-~ /-\ ,~- / \
3 ._.
S/O H
.. :~ : :
~`'',',' ~ ~
`
, . . .
~!, ,.~
~./-\.,~-. ~
::.: .. :, :: :. ,: . .-:
- : . .
: :, .: , : , : :
:, : : - . :::::: :
: :- :'::: .': : : . -::, ' :` :
. .
~ ~--SO H
HO3S--~ ~--N=N--~ ~--NH2 SO3H ~OCH3 t~ t-N=N--\ ~ N 2 SO;H 3 . ~ ~
-- ~ ,:
:, \, / ._.
/ \--N=H~ --NH
i il ~i-N=N--~ ~--NH
HO S/ ~ O/CH3 ~SO3H
\ /
/ \--N-N--~ ~--NH
O~H3 ~ ~ N=N--~ ~--NH2 - S~;H
- ~Cl HO
HO3S--~ ~.-N-N-~ /NH2 - :. :
~L$~ 3 HO
\ ~--N=N- t~ T'N 2 3 SO;H
OH
Ho-C2H40--~ ~.-N-N-t il t HO
._ . . .
103H ~OCH3 t~ t-N=N;--~ NH
t~
t iI t N-N--~ ~--NH2 ~03E
t-NSN--~ ~--NH2 :. /-~ /-\ ,~- / \
3 ._.
S/O H
.. :~ : :
~`'',',' ~ ~
`
, . . .
~!, ,.~
~./-\.,~-. ~
::.: .. :, :: :. ,: . .-:
- : . .
: :, .: , : , : :
:, : : - . :::::: :
: :- :'::: .': : : . -::, ' :` :
. .
Claims (15)
1. A stable concentrated dyestuff solution, containing, on a weight basis, (a) about 10 to about 50 % of a dyestuff of the formula where E is SO3H;
E' is SO3H or COOH; and A, A', B ant B' are each independently a naphthylene or phenylene group, unsubstituteted except by E and E' or further substituted by one or two groups, one of which is selected from the group consisting of hydroxy, nitro, cyano, trifluoromethyl, carboxy and SO3M, where M is K, Na, Li or H and/or one or two is selected from the group consisting of lower alkyl, lower alkoxy, hydroxyloweralkyl, hydroxyloweralkoxy and halogen, (b) about 20 to about 90 % water, (c) about 0.1 to about 1.0 % Li (d) less than about 1.5 % Na or K and (e) about 3 to about 15 % of an alkanolamine of the formula where X, Y and Z are each independently loweralkyl substituted with at least one hydroxy group, loweralkoxy-loweralkyl substituted with at least one hydroxy group, or C1-C4 alkyl, provided that no more than two of X, Y and Z are C1-C4 alkyl.
E' is SO3H or COOH; and A, A', B ant B' are each independently a naphthylene or phenylene group, unsubstituteted except by E and E' or further substituted by one or two groups, one of which is selected from the group consisting of hydroxy, nitro, cyano, trifluoromethyl, carboxy and SO3M, where M is K, Na, Li or H and/or one or two is selected from the group consisting of lower alkyl, lower alkoxy, hydroxyloweralkyl, hydroxyloweralkoxy and halogen, (b) about 20 to about 90 % water, (c) about 0.1 to about 1.0 % Li (d) less than about 1.5 % Na or K and (e) about 3 to about 15 % of an alkanolamine of the formula where X, Y and Z are each independently loweralkyl substituted with at least one hydroxy group, loweralkoxy-loweralkyl substituted with at least one hydroxy group, or C1-C4 alkyl, provided that no more than two of X, Y and Z are C1-C4 alkyl.
2. The stable concentrated dyestuff solution of claim 1, wherein the dyestuff is of the formula wherein R1, R2, R3 and R4 are each the same or different in each occurrence;
R1, R2, R3 and R4 are each independently hydrogen, methyl, methoxy, ethoxy, hydroxyethyl, hydroxyethoxy or chlorine, provided that no more than one of R1, R2, R3 and R4 is hydroxy or SO3M; and X, Y and Z
are independently methyl or hydroxyloweralkyl or hydroxyloweralkoxy-alkyl, provided that no more than two of X, Y and Z are methyl.
R1, R2, R3 and R4 are each independently hydrogen, methyl, methoxy, ethoxy, hydroxyethyl, hydroxyethoxy or chlorine, provided that no more than one of R1, R2, R3 and R4 is hydroxy or SO3M; and X, Y and Z
are independently methyl or hydroxyloweralkyl or hydroxyloweralkoxy-alkyl, provided that no more than two of X, Y and Z are methyl.
3. The stable concentrated dyestuff solution of claim 2, wherein X, Y and Z are each independently methyl, hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2,3-dihydroxypropyl or hydroxyethoxyethyl.
4. The stable concentrated dyestuff solution of claim 3, wherein the alkanolamine is triethanolamine, N-methyldiethanolamine or N,N-dimethylethanolamine.
5. The stable concentrated dyestuff of claim 4, wherein E-A-N=N-B- and -B'-N=N-A'-E' are selected from the group consisting of and or -B'-N=N-A'-E' is where R5 is H, hydroxy, methyl, methoxy or chloro.
6. The stable concentrated dyestuff solution of claim 5, wherein E-A-N=N-B- and -B'-N=N-A'-E' are selected from the group consisting of where R3 is H or methyl and
7. The stable concentrated dyestuff solution of claim 5, wherein E-A-N=N-B- and -B'-N=N-A'-E' are selected from the group consisting of and
8. The stable concentrated dyestuff solution of claim 5, wherein E-A-N=N-B- is and -B'-N=N-A'-E' is
9. A process of making a stable concentrated dyestuff solution, comprising the step of reacting phosgene with an aqueous solution of an alkanolamine salt of an aminoazo compound of the formula E-A-N=N-B-NH2, alone or mixed with no more than 50 mole-% of an aminoazo compound of the formula E'-A'-N-N-B'-NH2, at a temperature of 35°C to 60°C, while maintaining the pH of the reaction solutionat a value in the range of 5.0 to 8.5 with a lithium base alone or in combination with no more than 35 % of triethanolamine, N-methyl-diethanolamine or N,N-dimethylethanolamine; wherein E is SO3H;
E' is SO3H or COOH; and A, A', B and B' are each independently a naphthylene or phenylene group, unsubstituted except by E and E' or further substituted by one or two groups, one of which is selected from the group consisting of hydroxy, nitro, cyano, trifluoromethyl, carboxy and SO3M, where M is K, Na, Li or H and/or one or two is selected from the group consisting of lower alkyl, lower alkoxy, hydroxyloweralkyl, hydroxyloweralkoxy and halogen, and wherein the alkanolamine is of the formula where X, Y and Z are each independently loweralkyl substituted with at least one hydroxy group, loweralkoxy-loweralkyl substituted with at least one hydroxy group, or C1-C4-alkyl, provided that no more than two of X, Y and Z are C1-C4-alkyl.
E' is SO3H or COOH; and A, A', B and B' are each independently a naphthylene or phenylene group, unsubstituted except by E and E' or further substituted by one or two groups, one of which is selected from the group consisting of hydroxy, nitro, cyano, trifluoromethyl, carboxy and SO3M, where M is K, Na, Li or H and/or one or two is selected from the group consisting of lower alkyl, lower alkoxy, hydroxyloweralkyl, hydroxyloweralkoxy and halogen, and wherein the alkanolamine is of the formula where X, Y and Z are each independently loweralkyl substituted with at least one hydroxy group, loweralkoxy-loweralkyl substituted with at least one hydroxy group, or C1-C4-alkyl, provided that no more than two of X, Y and Z are C1-C4-alkyl.
10. The process of claim 9, wherein the pH is maintained with the lithium base alone.
11. The process of claim 10, wherein the lithium base is lithium hydroxide.
12. The process of claim 11, wherein the alkanolamine is. triethanol-amine, N-methyldiethanolamine or N,N-dimethylethanolamine.
13. The process of claim 12, wherein E-A-N=N-B- and -B'-N=N-A'-E' are selected from the group consisting of where R3 is H or methyl and
14. The process of claim 12, wherein E-A-N=N-B- and -B'-N=N-A'-E' are selected from the group consisting of and
15. The process of claim 12, wherein E-A-N=N-B- is and -B'-N=N-A'-E' is
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US79990977A | 1977-05-23 | 1977-05-23 | |
| US799,909 | 1985-11-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1112003A true CA1112003A (en) | 1981-11-10 |
Family
ID=25177072
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA303,730A Expired CA1112003A (en) | 1977-05-23 | 1978-05-19 | Disazo urea dyestuff solutions |
Country Status (6)
| Country | Link |
|---|---|
| BR (1) | BR7803289A (en) |
| CA (1) | CA1112003A (en) |
| DE (1) | DE2822318A1 (en) |
| ES (1) | ES470514A1 (en) |
| FR (1) | FR2392086A1 (en) |
| GB (1) | GB1603728A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3064342D1 (en) * | 1979-01-18 | 1983-09-01 | Ciba Geigy Ag | Stable concentrated solution of a disazo dye, process for its preparation and use of this solution |
| IN163246B (en) * | 1985-08-16 | 1988-08-27 | Atul Products Ltd | |
| IN163247B (en) * | 1985-08-16 | 1988-08-27 | Atul Products Ltd |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2051303C3 (en) * | 1970-10-20 | 1978-12-21 | Bayer Ag, 5090 Leverkusen | Polyhydroxyalkylamine salts of anionic dyes |
| CH556902A (en) * | 1970-10-22 | 1974-12-13 | Ciba Geigy Ag | PROCESS FOR THE PRODUCTION OF COLORS IN THE FORM OF STABLE CONCENTRATED SOLUTIONS OR DISPERSIONS. |
| US4002424A (en) * | 1973-06-14 | 1977-01-11 | E. I. Du Pont De Nemours And Company | Solution of isomer mixture of naphthylazophenylazonaphthyl disulfonate dye |
-
1978
- 1978-05-19 CA CA303,730A patent/CA1112003A/en not_active Expired
- 1978-05-22 ES ES470514A patent/ES470514A1/en not_active Expired
- 1978-05-22 DE DE19782822318 patent/DE2822318A1/en not_active Withdrawn
- 1978-05-22 GB GB2124878A patent/GB1603728A/en not_active Expired
- 1978-05-22 FR FR7815147A patent/FR2392086A1/en not_active Withdrawn
- 1978-05-23 BR BR7803289A patent/BR7803289A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| FR2392086A1 (en) | 1978-12-22 |
| GB1603728A (en) | 1981-11-25 |
| ES470514A1 (en) | 1979-09-01 |
| DE2822318A1 (en) | 1978-12-14 |
| BR7803289A (en) | 1979-01-16 |
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