US3520871A - Mixtures of phenyl-azo-phenyl dyestuffs and process for preparing same - Google Patents

Mixtures of phenyl-azo-phenyl dyestuffs and process for preparing same Download PDF

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Publication number
US3520871A
US3520871A US673956A US3520871DA US3520871A US 3520871 A US3520871 A US 3520871A US 673956 A US673956 A US 673956A US 3520871D A US3520871D A US 3520871DA US 3520871 A US3520871 A US 3520871A
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grams
dyestuff
mixture
phenyl
dyestuffs
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Dominic A Zanella
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American Aniline Products Inc
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American Aniline Products Inc
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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
    • C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
    • C09B67/0046—Mixtures of two or more azo dyes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/92—Synthetic fiber dyeing
    • Y10S8/922—Polyester fiber
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/933—Thermosol dyeing, thermofixation or dry heat fixation or development

Definitions

  • Such fibers may be prepared by heating a glycol of the formula HO(CH OH wherein n is an integer greater than 1 but not exceeding 10 with isophthalic or terephthalic acid or with an ester-forming derivative thereof, for example, an aliphatic or aryl ester or half ester, an acid halide or an ammonium or an amine salt under conditions at which polycondensation is effected.
  • Such fibers are available under the trademarks Dacron and Terylene, for example, and have made a remarkable impact on the textile industry.
  • Polyesters are conveniently dyed with dispersed dyes (excluding solvent dyeing methods) by carrier dyeing, pressure dyeing, and by thermofixation methods such as the Thermosol process.
  • carrier dyeing excluding solvent dyeing methods
  • the widely used carrier dyeing technique involves the preparation of a dyebath containing amout 0.5-1 grams per liter of a dispersing agent and about 3-5 grams per liter of a phosphate such as monosodium phosphate or diammonium phosphate.
  • the polyesters fabric to be dyed is then added to the dyebath.
  • .bath is heated to 50-60 C. and maintained at that temo perature for about minutes.
  • To the dyebath containing the fabric is then added about 3-5 grams per liter of a carrier such as o-phenylphenol, and the fabric is allowed to absorb the carrier for about 15 minutes at 50 C.
  • a carrier such as o-phenylphenol
  • Thermosol process which involves the use of controlled heat, such as hot air or heated coils, is also used for dyeing polyesters and mixed fabrics containing those fibers.
  • a dispersed dye is padded onto the fabric and then thermofixed by heating the temperatures to 180220 C. (cf. 360-425 F.) for 30-90 seconds.
  • temperatures slightly lower i.e.
  • the third commerciallyimportant methodof dyeing polyester fabrics is pressure dyeing. This process involves dyeing the fabric under pressure in an aqueous dyebath at a temperature above the normal boiling point of the dyebath. Pressure dyeing has certain advantages over other dyeing processes; for example, no carrier is usually required, and dyeing time is reduced.
  • a dyestuff should also dye polyesters with little or no variation in shade with a variation in the dyeing method.
  • dyestuffs for polyesters which are prepared from a tertiary amine coupling compound containing two hydroxyalkyl groups which have been modified and an appropriate diazo component.
  • Such dyestuffs have proven to have good affinity for polyester fibers under certain conditions.
  • one such modification is the diacetoxy derivative of a tertiary amine coupling component containing two hydroxyalkyl groups prepared by acylation with acetyl chloride, cf. US. 3,178,405.
  • the size of the dyestuff molecule is increased by an increase in molecular weight of the acylating agent, the effectiveness of the dyestuff as a polyester dye diminishes rapidly.
  • a dyestuff comprising a complex mixture of mono-esters and diesters.
  • the complex mixture consists essentially of the components:
  • R R R X, Y, Z, and n have the meanings aforesaid.
  • the relative proportions of the components A, B, and C are such that component B comprises at least about 25 mole percent of the mixture and component C comprises no more than about 25 mole percent of the mixture.
  • the dyestuffs of my invention are prepared by coupling with a diazotized arylamine a coupling component comprising a complex mixture of di-ester and monoesters of a 3-bis(hydroxyalkyl)aminoacetanilide.
  • R R R R and n have the meanings aforesaid.
  • the complex ester mixture coupling component is prepared by reacting a 3-bis(hydroxyalkyl)aminoacetanilide with both an aromatic acylating agent and an aliphatic acylating agent in order to esterify the hydroxyalkyl groups of the molecule.
  • aromatic acylating agents are benzoyl chloride, o-chlorobenzoyl chloride, p-chlorobenzoyl chloride, anisoyl chloride, toloyl chloride, or an acid derivative thereof, e.g. benzoic acid.
  • Suitable aliphatic acylating agents are those having from 2-5 carbon atoms such as acetyl chloride, butyryl chloride, propionyl chloride, chloroacetyl chloride, or an acid or anhydride derivative thereof, e.g. butyric acid, chloroacetic acid, w-chlorobutyric acid, or butyric anhydride. From a standpoint of a yield and product purity, the acyl halides are generally preferred.
  • the quantity of aromatic acylating agent reacted with the substituted acetanilide is from about 75 mole percent based on the theoretical amount required to esterify the hydroxyalkyl groups present in the molecule.
  • the quantity of aliphatic esterifying agents employed is at least an amount to insure that no unreacted bis(hydroxyalkyl)amino-groups remain in the reaction mixture and to also insure that no more than about 25% of the components in the complex ester mixture correspond to Formula C.
  • the dyestuffs of my invention may be prepared by coupling the mixed ester-coupling component described above into a diazotized arylamine in an aqueous medium and recovering the dyestuff formed therefrom by filtration.
  • the dyestuffs may be prepared by coupling the 3-bis(hydroxyalkyl)aminoacetanilide into a diazotized arylamine and thereafter esterifying the azo reaction product with both an aromatic and aliphatic esterifying agent in an inert solvent such as monochlorobenzene. Regardless of which method is employed, thin-layerchromatographic analysis of the dyestuffs shows that they are complex mixtures.
  • That method of analysis separates the dyestuff into its various components and involves first preparing a 5% solution of the dyestuff in acetone. Four (4) microliters of the solution are spotted on a glass plate on which has been previously cast a 250 micron layer of silica gel. After drying, the spot is eluted with a 4/1 by volume benzene/acetone solution. As the dyestuff spot migrates vertically up the plate, the various components of the dyestuff separate. That is, depending upon its polarity, relative solubility, etc., in the elution liquid, each component will migrate to a different height on the plate.
  • dyestuffs prepared according to my invention are a complex mixture consisting essentially of dyestuffs designated hereinbefore A, B, and C with small amounts of di-aryl ester and di-aliphatic ester, and perhaps trace quantities of unesterified material.
  • the relative proportions of the dyestuff components A, B, and C as derived from mixed ester coupler components A, B, and C, respectively, are quite critical if the dyestuff is to be a good, all-purpose dye, that is, a dye which may be applied with good results by pressure dyeing, carrier dyeing, and thermofixation methods. I have found that at least about 25%, preferably about of the mixture must correspond to that dyestuff designated B, and no more than about 25% of the mixture should correspond to that dyestuff designated C. Dyestuif mixtures containing less than about 25% B or more than about 25% C exhibit less than satisfactory light fastness; and,
  • the complex mixture dyestulf of my invention surprisingly has significantly improved dyeing properties over any of its components taken individually. I find that pure dyestuff A does not build up well on polyester fibers and is, therefore, difiicult to apply by conventional methods. Pure dyestuff B exhibits inferior light fastness when compared to the complex ester mixture dye. Pure dyestuff C likewise is inferior to the mixture in both build up and light fastness.
  • the desired degree of esterification and, consequently, the kind of mixed ester dyestuff of my invention is obtained by regulating the amount of aromatic and aliphatic acylating agent used in preparing the mixed ester, whether before or after the coupling reaction.
  • at least about 25% of the mixture should correspond to Formula B, the monoaromatic ester, monohydroxy component. I find that this requires esterification with at least about 40% of the theoretical amount of aromatic esterifying agent, e.g. benzoyl chloride, based on the total hydroxycontent of the molecule to be esterified.
  • the maximum amount of aliphatic esterifying agent employed depends on the esterification procedures used to prepare the mixed ester, and also on the amount of aromatic esterifying agent used.
  • the mixed diester coupler of my invention may be conveniently prepared by reacting a 3-bis-(hydroxyalkyl)aminoacetanilide with both an aromatic and aliphatic esterifying agent in the presence of an inert solvent such as monochlorobenzene.
  • the 3-bis(hydroxyalkyl)aminoa'cetanilide is added to from 2-5 parts by weight solvent, and the esterifying agents are added thereto at a temperature of from -60-120 C.
  • the reaction mixture is held on temperature for from 1-3 hours after all the esterifying agents have been added.
  • a suitable ester mixture is prepared by first adding dropwise to the solvent containing the substituted acetanilide from 4075% of the theoretical amount of aromatic esterifying agent required to esterify the total hydroxy groups present. After the addition of the aromatic esterifying agent, I add the aliphatic esterifying agent to the mixture.
  • the amount of aliphatic esterifying agent used varies from as little as 15 of the theoretical amount required based on hydroxy groups to be esterified when 65% or more aromatic agent is used to as much as 40% when lesser amounts of aromatic agent are used.
  • the aliphatic esterifying agent is used as solvent and reactant.
  • This method involves first preparing a mixture of aliphatic and aromatic agents, the aliphatic agent being present in about 1-2 parts by weight based on the 3-bis(hydroxyalkyl)-aminoacetanilide, and the aromatic agent being present in 4075% of theoretical amount required to esterify the total hydroxyalkylgroups on the acetanilide. To the mixture of esterifying agents is then added the 3-bis-(hydroxyalkyl) aminoacetanilide, and the resulting mixture is reacted at 60-100 C. for one to three hours.
  • the product contains at least about 10% of monoaliphatic ester, monohydroxy component (corresponding to Formulas C and C) when higher amounts (60%) of aromatic esterifying agent are used with minimum amounts of aliphatic esterifying agent or when an aliphatic acid is used as solvent. Greater amounts of that compound are, of course, obtained when greater amounts of aliphatic esterifying agent are used with lesser amounts of aromatic esterifying agent.
  • the reaction product contains as much as about 65 mole percent rmonoaromatic ester, monohydroxy component (corresponding to Formulas B and B), and about 10 percent monoaliphatic ester, monohydroxy component (corresponding to Formulas C and C).
  • the remaining portion of the mixture corresponds to the mixed aromatic, aliphatic diester (corresponding to Formulas A and A).
  • the proportions of the various products vary, of course, 'with varying amounts of aromatic and aliphatic esterifying agents.
  • Aryl amines useful as diazo components of the dyestulfs according to my invention may be diazotized by any conventional means.
  • the p-nitroaniline is dissolved in dilute HCl.
  • blue monazo dyestuffs provided by my invention which may be prepared by coupling the mixed ester coupling component designated hereinbefore A, B, and C into diazotized 2,4-dinitro6-bromoaniline.
  • These blue dyestuffs may be mixed with appropriate shading components, e.g. oranges, to prepare black dyestuffs.
  • the dyestuffs of my invention may be standardized either as a dispersed paste or a dispersed powder by any of the basic standardizing techniques that have been known to the art for many years; i.e. by the use of appropriate amounts of dispersants and standardizing agents, usually together with small amounts of anionic wetting agents to assist in dispersion.
  • Standardized pastes are made by wet milling the dye in conventional equipment in the presence of the dispersing agent, such as sodium lignin sulfonate or sodium alkylnaphthalene sulfonate.
  • the dispersing agent such as sodium lignin sulfonate or sodium alkylnaphthalene sulfonate.
  • Other useful commercially available dispersing agents such as the sodium salts of carboxylated polyelectrolytes and the naphthalene sulfonates may also be used as dispersants.
  • the dispersed paste is cut or standardized to a standard strength with a diluent, such as sodium sulfate or dextrin.
  • the final color content of the finished paste averages from l--40% by weight active dyestutf base (pure color).
  • Standardized dispersed powders are prepared by wet milling the dyestuff in the presence of a dispersant, such as those mentioned here-above, in equipment such as a ball mill, Werner-pileiderer mill or attritor.
  • the dispersed material is dried and micropulverized, or spray dried usually in the presence of a diluent such as sodium sulfate to provide the dispersed powder.
  • a wetting agent such as sodium cetyl sulfate or an alkyl phenoxy polyoxyethanol may be added to the product.
  • a mixed ester coupler was prepared as follows: To a SOO-ml. flask was charged 50 grams butyric acid and 29 grams benzoyl chloride. The mixture was heated to 70 C. and at 70-75 C. during one hour was added 56.4 grams (0.2 mole) 3 bis(hydroxyethyl)amino-4- ethoxyacetanilide. The reaction mass was held at 70-75 C. for two hours and then poured into a beaker containing 600 grams ice, 600 grams water, 40 grams 32% HCl, and 5 grams dispersant.
  • a dispersion was prepared containing 15% of the dyestulf and sodium lignin sulfonate dispersant together with a small amount of glycerine and sufficient water to bring the solids content of the dispersion to 50% by weight.
  • the paste thus prepared was then wet-milled until the dyestutf was sufficiently dispersed.
  • Dacron polyester fabric was pressure dyed at 2,4, and 8% dyestulf levels in a dye bath containing 1% monosodium phosphate. The dyeings were done in a closed vessel at 240 C. for 60 minutes. The dyed fabric was of the same shade as the fabric dyed by the carrier method described above, that is, a navy blue. The dyeings had excellent sublimation fastness, good fastness to light, reserved cotton and wool, and built up proportionately in strength with the amount of color in the dye bath.
  • Dacron polyester fabric was dyed with the dispersed dyestuff prepared above by the Thermosol process at 400 F. 2,4, and 8%.
  • the dyeings built up in strength proportionately to the amount of dyestuff applied and were of substantially the same shade and fastness characteristics of the dyeings made by the carrier and pressure dyeing methods above.
  • Example III The method of Example I was repeated with the exception that 35.0 grams p-anisoyl chloride was used in place of the benzoyl chloride.
  • the dyestuff prepared was slightly greener in shade than that of Example II with substantially equal fastness and dyeing properties.
  • Example IV The method of Example I was repeated with the exception that 37.0 grams O-chlorobenzoyl chloride was used in place of the benzoyl chloride. A navy blue dyestuff with substantially the same fastness and dyeing properties as that of Example I was prepared.
  • Example V The method of Example I was repeated with the exception that 33 grams p-methylbenzoyl chloride was used in place of the benzoyl chloride. A navy blue dyestutf substantially the same as that of Example I was prepared.
  • EXAMPLE VI The method of Example 11 was repeated with the exception that 54 grams 3 bis(hydroxyethyl)amino 4- methoxybutyranilide was used in place of the 3-bis(hydroxyethyl)amino-4-ethoxyacetanilide.
  • the dyestutf prepared was navy blue in shade and had fastness and dyeing properties substantially the same as the dyestuff of Example II.
  • Example VIII The method of Example II was repeated with the exception that 37 grams benzoyl chloride and 16.8 grams hutyryl chloride were used. The dyestuif prepared dyed polyester fabric slightly greener than that of Example II.
  • EXAMPLE XI having 14 carbon atoms or a chloro-lower alkyl radical
  • a 500 cc. flask equipped with mechanical agitator was charged 200 grams anhydrous monochlorobenzene, 56.5 grams benzoyl chloride, 45.0 grams monochloroacetic acid.
  • the mixture was stirred and heated to 65 C. and at 6570 C. was added 56.4 grams 3-bis(hydroxyethyl)amino-4-ethoxyacetanilide.
  • the mixture was stirred 2 hours at 6570 C. and was then poured into a beaker containing 600 grams water and 40 grams 32% HCl. Two liquid layers were formed and the monochlorobenzene layer was separated from the aqueous phase by decantation.
  • the aqueous layer was iced to C. and there was added thereto 52.4 grams 2,4-dinitro-6bromoaniline previously diazotized in the manner of Example I.
  • the dyestuff prepared dyed polyester fabric
  • the dyestuff comprising a complex mixture of esters consisting essentially of the components:
  • R is phenyl, lower alkyl-phenyl, lower alkoxyphenyl or chloro-phenyl;
  • R is a lower alkyl radical having 1-4 carbon atoms;
  • R is a lower alkyl radical having from 1-3 carbon atoms;
  • R; is H or lower alkoxy;
  • X is N0 Cl, Br, H, S0 lower alkyl, SO NH CONH COO lower alkyl, CN or CF
  • Y is N0 CN, S0 lower alkyl, or NHCOCH Z is H, Cl, Br, N0 or CN; and
  • n has a value of 1-2;
  • component B comprising at least about 25 mole percent of the mixture, and component C comprising no more than about 25 mole percent of the mixture.
  • component B comprises at least about 50 mole percent of the mixture.
  • R is phenyl, lower alkyl-phenyl, lower alkoxyphenyl or chloro-phenyl; R is H or lower alkoxy;
  • X is N0 Cl, Br, H, S0 lower alkyl, SO NH CONH COO lower alkyl, CN or CF
  • Y is N0 or CN;
  • Z is Cl, Br, N0 or CN; and
  • n has a value of 1-2.

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  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
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US673956A 1967-10-09 1967-10-09 Mixtures of phenyl-azo-phenyl dyestuffs and process for preparing same Expired - Lifetime US3520871A (en)

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US (1) US3520871A (enrdf_load_stackoverflow)
CH (1) CH492762A (enrdf_load_stackoverflow)
DE (1) DE1769085A1 (enrdf_load_stackoverflow)
ES (1) ES350745A1 (enrdf_load_stackoverflow)
FR (1) FR1572880A (enrdf_load_stackoverflow)
GB (1) GB1227871A (enrdf_load_stackoverflow)
NL (1) NL6801942A (enrdf_load_stackoverflow)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3936266A (en) * 1974-02-11 1976-02-03 Allied Chemical Corporation Trihalo monoazo dyestuffs
US4254027A (en) * 1975-07-28 1981-03-03 Imperial Chemical Industries Limited Disperse monoazo dyestuffs for coloring synthetic textile materials
US4769449A (en) * 1985-03-30 1988-09-06 Cassella Aktiengesellschaft Red mono-azo water-soluble dye containing cyano, amide and amino substituents
CN117756658A (zh) * 2023-12-07 2024-03-26 浙江迪邦化工有限公司 一种红玉酯化液连续化制备的工艺及系统

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2171110A (en) * 1985-02-16 1986-08-20 Yorkshire Chemicals Plc Monoazo disperse dyes

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2283327A (en) * 1937-09-18 1942-05-19 Soc Of Chemical Ind Azo dyestuffs
US3178405A (en) * 1956-07-25 1965-04-13 Merian Ernest Water-insoluble monoazo dyestuffs
US3268507A (en) * 1962-08-10 1966-08-23 Bayer Ag Water-insoluble monoazo dyestuffs

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2283327A (en) * 1937-09-18 1942-05-19 Soc Of Chemical Ind Azo dyestuffs
US3178405A (en) * 1956-07-25 1965-04-13 Merian Ernest Water-insoluble monoazo dyestuffs
US3268507A (en) * 1962-08-10 1966-08-23 Bayer Ag Water-insoluble monoazo dyestuffs

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3936266A (en) * 1974-02-11 1976-02-03 Allied Chemical Corporation Trihalo monoazo dyestuffs
US4254027A (en) * 1975-07-28 1981-03-03 Imperial Chemical Industries Limited Disperse monoazo dyestuffs for coloring synthetic textile materials
US4769449A (en) * 1985-03-30 1988-09-06 Cassella Aktiengesellschaft Red mono-azo water-soluble dye containing cyano, amide and amino substituents
US4908042A (en) * 1985-03-30 1990-03-13 Buehler Ulrich Process for coloring cellulose on polyester with water-insoluble red mono-azo dyes
CN117756658A (zh) * 2023-12-07 2024-03-26 浙江迪邦化工有限公司 一种红玉酯化液连续化制备的工艺及系统

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DE1769085A1 (de) 1971-09-16
FR1572880A (enrdf_load_stackoverflow) 1969-06-27
CH492762A (de) 1970-06-30
NL6801942A (enrdf_load_stackoverflow) 1969-04-11
ES350745A1 (es) 1969-11-16
GB1227871A (enrdf_load_stackoverflow) 1971-04-07

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