PL153577B2 - Method for producing chromium complex dyes type 1:1 - Google Patents

Description

PATENT DESCRIPTION

Additional patent to patent no. ----- Pending: ea 03 07 (p. 27ioa?)

Priority ---- Application announced: aa 12 oa

Patent description published: 1991 09 30

153 577

Int. Cl.® C09B 29/15

C09B 45/16

CZHEIIU

OCÓIU

Creators of the invention: Lucjan Szuster, Andrzej Gawłowski

Authorized by the patent: Research and Development Center

The Organika Dye Industry,

Zgierz (Poland)

METHOD OF OBTAINING CHROMOCOMPLEX DYES TYPE 1: 1

The subject of the invention is a process for the preparation of 1: 1 chromocomplex dyes of the general formula 1, in which A represents a residue of the general formula 2, in which R 5 represents a hydrogen atom or a nitro group, and Y represents a hydrogen, sodium, potassium atom or an ammonium or ammonium group or A represents a residue of the general formula 3 in which R ₂ is a hydrogen or chlorine atom or a nitro group, B is a residue of the formula 4, 5 or 6, and X is an anion Cl ", SO 4 -, HSO 4" or HCOO. They are used to dye wool or polyamide fibers and leather, depending on the monoazo dyes used for their production, into the colors of orange, red, purple, navy blue or black, and to produce chromo complex dyes type 1: 2 and 2: 3.

A known method is used to obtain 1: 1 chromocomplex dyes of the general formula 1, in which the symbols have the above meanings, by chromating the corresponding o'-dihydroxymonazo dyes with sulfate or basic chromium sulfate in an acid medium from sulfuric acid at a temperature of 125-15 □ C under pressure for 20 hours (Polish Patent No. 35,572).

□ the said chromocomplex dyes are also obtained by chromating the corresponding o-dihydroxymonase dyes with sulfate or basic chromium sulfate in the presence of preferably up to 1 mole of salicylic acid as a chromium carrier, per 1 mole of monoazo dye, at pH 2-3, at a temperature of 95-100 * C, within 3 hours (NRO Patent No. 148,783).

There is also a known method of obtaining chromocomplex dyes of the 1: 1 type, consisting in heating suspensions of appropriate monoazo dyes with chromium formate in an aqueous medium, at pH 1-4, at a temperature of 105-135 * C, under pressure of 150-400 kPa (BIOS No. 961 , pp. 159, 164-166, 168).

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Said monoazo dyes are obtained, as is known, by coupling 1-azo-2-oxynaphthalen- or -benzenesulfonic acids and their nitro and chlorine derivatives with 1 or 2-naphthol or with 1-phenyl-3-methylpyrazolone-5.

According to the prior art in the field of chemistry and production technology of the azo dyes in question, complete dissolution of 1- or 2-naphthol or phenylpyrazolone in a strongly alkaline environment before the coupling process was considered a necessary condition for the proper course of the coupling. Therefore, in the coupling processes known to date with 1- or 2-naphthol or with phenylpyrazolone, separately strongly alkaline solutions of the above-defined passives were prepared, which were used for the coupling reaction in this form, optionally subjected to acidification prior to the coupling.

In known processes for the production of monoazo dyes using 1- or 2-naphthol as the passive component, including also o, o'-dihydroximonoase dyes of the formula HA-N = N-BH, in which A is as defined above and B is the residue 4 or 5, 1 or 2-naphthol is used in the form of sodium naphtholates and the coupling reaction is carried out in a strongly alkaline medium (e.g. BIOS No. 961, p. 168). In the production of monoazo dyes using phenylpyrazolone as inactive component, it is also used in the form of the sodium salt in known processes (BIOS No. 961, pp. 164, 166).

There is also a known process for the preparation of azo dyes and pigments, described in US Patent No. 4,395,264. This process uses 2-naphthol or its substituted derivatives as passive components, and various aromatic or aliphatic amines optionally substituted in the ring are used as active ingredients. with one or more substituents such as, for example, chlorine or bromine atoms or nitro, alkyl, alkoxy, cyano, carboxyl, ketone, arylazo, acylamino, sulfo or onium groups. This method does not demonstrate the preparation of o'-dihydroxyazo dyes, capable of forming complexes with metals. In this way, 2-naphthol is dissolved separately while hot with a strong base (at pH 10-12), precipitated with strong acid (at pH 0.5-2), and then the mass containing the 2-naphthol suspension is cooled to 0- 15 * C. The mass containing the diazo compound of the active ingredient is introduced into the mass containing the inert component suspension obtained as described above, and then the pH of the reaction medium is first adjusted to a value of 1-4 with a strong base and then to a value of 5-10 with a weak base. The process of alkalizing the mixture of active and passive ingredients in this method is a two-stage process.

It has surprisingly been found that the coupling reaction of 1-azo-2-oxynaphthalen- or -benzenesulfonic acids and their nitro and chloro derivatives with 1- or 2-naphthol or with 1-phenyl-3-methylpyrazolone-5 can be carried out using the above-mentioned passives in their acid forms without pre-dissolving them in a highly alkaline medium and by subjecting the mixture of active and passive suspensions prior to coupling to acid pretreatment, thereby obtaining a number of technological advantages as defined below.

The method according to the invention produces 1: 1 chromocomolex dyes of the general formula 1, in which the symbols have the above meanings, by coupling 1-azo-2-oxynaphthalenesulfonic acid-4,1-azo-2-oxy-α-nitronaphthalenesulfonic acid- 4,1-azo-2-oxybenzenesulfonic-5,1-azo-2-oxy-5-nitrobenzenesulfonic-3,1-azo-2-oxy-5-chlorobenzenesulfonic-3,1-azo-2-oxy-3 -nitrobenzenesulfonic-5 or 1-azo-2-oxy-3-chlorobenzenesulfonic-5 with 1- or 2-naphthol or with 1-phenyl-3-methylpyrazolone-5 in an aqueous medium and chromating the obtained monoazo dye of general formula ΗΑ-Ν -Ν-ΘΗ, in which the symbols have the above meanings, in an aqueous medium, with trivalent chromium used in an amount not less than 1 gram of chromium per 1 mole of monoazo dye. In this process, a mixture containing 1-azo-2-oxynaphthalenesulfonic acid-4,1-azo-2-oxy-6-nitronaphthalenesulfonic acid-4,1-azo-2-oxybenzenesulfonic acid-5,1-azo-2-oxy suspensions is applied. -5-nitrobenzenesulfonic-3,1-azo-2-oxy-5-chlorobenzenesulfonic-3, 1-azo-2-oxy-3-nitrobenzenesulfonic-5 or 1-azo-2-oxy-3-chlorobenzenesulfonic-5 and acid

153 577 forms of 1- or 2-naphthol or 1-phenyl-3-methylpyrazolone-5, optionally in the presence of hydrotropic agents, such as e.g. urea, thiourea, caprolactam and the like, and / or surfactants, such as anionic agents, such as e.g. 2-ethylhexyl sulfosuccinate, known as SBO Wetting Agent, or sodium salt of condensed polynuclear aromatic sulfonic acids, known as NNO-Dispersant, cationic agents, e.g., triethanolamine ester of stearic acid, known as IW Tenderizer, or nonionic agents, such as e.g. . polycondensation products of ethylene oxide, known as Polycols, or condensation products of ethylene oxide with phenol derivatives, known as Rokafenols, or condensation products of ethylene oxide with oleyl alcohol derivatives, known as Rokanols, or mixtures of these agents, e.g. the composition of the condensation product of caprolactam with triethanolamine and ethoxylated alkylphenol, known as Lodegalu KLN, pretreated by blending e at a pH below 2, then the medium is gradually alkalinized and the coupling reaction is carried out at pH 4-11, and the obtained monoazo dye with the general formula HA-N = N-BH is subjected, optionally after its separation from the coupling reaction medium, to chromium with the use of a trivalent chromium salt at a pH below 3. The method according to the invention may also initiate the chromation reaction at pH 3-9, and then subject the prepared mixture of a 1: 2 chromocomplex dye of the general formula 7, in which the symbols have the above-mentioned meanings, and the trivalent chromium salts and optionally a monoazo dye of general formula HA-N-N-BH and a 1: 1 chromocomplex dye of general formula 1 with further treatment of the trivalent chromium salt contained in the mixture at a pH below 3.

In the event that the chrome plating begins at pH 3-9, a mineral acid, preferably sulfuric acid, is optionally added as the monoazo dye disappears from the mixture. The addition of acid is carried out until the pH is below 3. The process is carried out in an aqueous medium under normal or elevated pressure, at the boiling point of the reaction mixture.

As a result of the coupling process according to the invention, monoazo dyes of the formula HA-N = N-BH are obtained, and then, by chromium plating, chromo complex dyes of the 1: 1 type, of the formula 1, with high yield and with a high degree of purity. The formation of a transiently well-soluble 1: 2 chromocomplex dye accelerates the production of a 1: 1 chromocomplex dye and allows the chrome plating process to be carried out in high concentrations, while avoiding the problems associated with mixing the reaction mass. The chromium plating according to the invention takes on average 3-5 hours without the use of salicylic acid.

The invention is illustrated by the following examples in which parts and percentages are parts and percentages by weight and degrees of temperatures are given in degrees Celsius:

EXAMPLE 1 To 100 parts of water at 65 * 29.5 parts of 1-azo-2-oxy-6-nitronaphthalenesulfonic acid-4-acid paste, 1.5 parts of caprolactam and 0.75 parts of Lodegal KLN are added. After mixing, 16 parts of 2-naphthol are added. The obtained suspension with a pH below 2 is stirred for 30 minutes at the temperature of 40-45 ', and then 26 parts of 30% of sodium hydroxide solution are added to the mixture containing red crystals of the addition product of the passive and active components to a pH in the range 7.0-7.5 . The obtained monoazo dye suspension is stirred until the presence of the diazonium compound disappears, then 13 parts of sulfuric acid are added to it to pH = 2, 13.5 parts of formic acid and 31 parts of basic chromium-sodium alum known as Chromal 0-33. The whole is heated at 115-120 ° C under 200 kPa pressure for 2 hours. The resulting dye is filtered off. A 1: 1 chromocomplex dye is obtained, dyeing woolen, polyamide and leather fibers black. This dye can also be used as an intermediate for the synthesis of 1: 2 or 2: 3 chromocomplex dyes.

Example II. The monoazo dye was prepared as described in Example 1, and the resulting dye suspension was filtered off after the disappearance of the diazonium compound. The resulting dye paste is spread in 100 parts of water with the addition of 31 parts for

153 577 of sodium chromium alum, known under the trade name Chromal 3-33, and heated to a temperature above 90 *. A slurry with a pH of 3.5-4 is obtained, containing a mixture of 1: 1 and 1: 2 chromocomplex dyes and the starting monoazo dye. 5 parts of sulfuric acid are added to this suspension to a pH below 3 and the whole is heated at 115-120 ° C under a pressure of 200 kPa. The reaction mixture was kept under these conditions for 2 hours. A 1: 1 chromocomplex dye is obtained, dyeing wool, polyamide and leather black. This dye can also be used as an intermediate for the synthesis of 1: 2 or 2: 3 chromocomplex dyes.

Example III. The monoazo dye was prepared as described in Example 1. To the obtained dye was added IB parts of chromium chloride without separating it from the solution and heated to a temperature above 90 ° C. A suspension of pH 3-3.5 containing a mixture of chromocomplex dyes of the 1: 1 and 1: 2 type and the starting monoazo dye is obtained. 5 parts of hydrochloric acid are added to the resulting mixture to a pH below 3 and it is heated under reflux for 6 hours. A 1: 1 chromocomplex dye is obtained, dyeing with wool, polyamide and leather black. This dye can also be used as an intermediate for the synthesis of 1: 2 or 2: 3 chromocomplex dyes.

Example IV. 15 parts of 5-1-phenyl-3-methylpyrazolone and 19.6 parts of 3-azo-2-oxy-5-nitrobenzenesulfonic acid are added to 200 parts of water at 30 ° C. The resulting mixture, with a pH below 2, is stirred for 15 minutes and made basic with 20 parts of sodium hydroxide to a pH between 6.5-7.5. The dye solution is stirred until the diazonium compound disappears. The obtained monoazo dye is chromated based on its separation from the medium after the diazotization reaction as described in Example 2. A 1: 1 chromocomplex dye is obtained, dyeing with wool, polyamide and leather in an orange color. This dye can also be used as an intermediate for the synthesis of 1: 2 or 2: 3 chromocomplex dyes.

EXAMPLE 5 25 parts of 1-azo-2-oxynaphthalenesulfonic acid-4-acid paste, 15 parts of 1-phenyl-3-methyl-5-pyrazolone and 1.5 parts of urea are added to 100 parts of water at 65 ° C. The resulting mixture with a pH below 2 is stirred for 15 minutes and made alkaline with 20 parts of 30 ° sodium hydroxide to a pH in the range 6.5-7.5. The solution is stirred until the importance of the diazonium compound disappears. The obtained monoazo dye is acidified with 20 parts of sulfuric acid to a pH below 3, 21 parts of chromium formate are added and the whole is heated at 115-120% under a pressure of 200 kPa, and then kept under these conditions for 2 hours. A 1: 1 chromocomplex dye is obtained which dyes wool, polyamide and leather purple. This dye can also be used as an intermediate for the synthesis of 1: 2 or 2: 3 chromocomplex dyes.

Example VI. To 200 parts of water, 10.7 parts of 5-1-azo-2-oxy-3-chlorobenzenesulfonic acid, 15 parts of 5-1-phenyl-3-methylpyrazolone, 1.5 parts of urea and 0.75 parts of SBO humidifier are added. The resulting suspension with a pH below 2 is stirred for 15 minutes and made alkaline IB with 30 parts of sodium hydroxide and 6 parts of soda to a pH of 6.5-7.5. The resulting solution is stirred until the importance of the diazonium compound disappears, heated to 80 ° C, salted out with 50 parts of sodium chloride and filtered. The obtained monoazo dye was suspended in 100 parts of water and chromated as described in Example 1. The obtained chromo complex dye type 1: 1 dyeing wool, polyamide and leather red. This dye can also be used as an intermediate for the synthesis of 1: 2 or 2: 3 chromocomplex dyes.

Example VII. To 100 parts of water at 65 ° C, 25 parts of 1-azo-2-oxynaphthalenesulfonic acid paste, 1 part of Rokanol 0-30 and 16 parts of 1-naphthol are added. After mixing, 26 parts of 30% sodium hydroxide solution are added to the suspension obtained with a pH below 2, to a pH of 6.5-7.5. The suspension is stirred until the importance of the diazonium compound disappears. The obtained monoazo dye is chromated, without being released from the medium after the diazotization reaction, according to the method described in Example III. A 1: 1 chromocomplex dye is obtained, dyeing wool, polyamide and leather navy blue. This dye can also be used as an intermediate for the synthesis of 1: 2 or 2: 3 chromocomplex dyes.

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Example VIII. To 100 parts of water at 65 'temperature, 29.5 parts of 1-azo-2-oxy-6-nitronaphthalenesulfonic acid-4 in the form of an acid paste, 1.5 parts of urea and 0.75 parts of SBO humidifier are added, and after mixing - 16 2-naphthol parts. The obtained suspension with a pH below 2 was stirred at 40-45 ° for 30 minutes. To the mixture containing red crystals of the addition product of the active and passive components, 26 parts of 30 sodium hydroxide solution are added within 30 minutes to a pH in the range of 6.5-7.0, and then - 4.2 parts of sodium bicarbonate. The temperature of the reaction medium spontaneously rises to about 60 *. The mixture is stirred under these conditions until the diazonium compound disappears. The pH of the mixture is 8.2-8.9. The obtained monoazo dye is separated by filtering off the precipitate. The monoazo dye paste is mixed with 250 parts of water and 31 parts of the basic chromium-sodium alum known as Chromal 3-33. The whole is heated in the temperature 115-120 ° under the pressure of 200 kPa and kept under these conditions for 3 hours. The resulting 1: 1 type chromium complex is isolated by filtering off the precipitate.

Claims (2)

Patent claims 1-azo-2-oxy-naphthalenesulfonic-4,1-azo-2-oxy-6-nitronaphthalenesulfonic-4,1-azo-2-oxybenzenesulfonic-5,1-azo-2-oxy-5-nitrobenzenesulfonic-3,1- azo-2-oxy-5-chlorobenzenesulfonic-3,1-azo-2-oxy-3-nitrobenzenesulfonic-5 or 1-azo-2-oxy-3-chlorobenzenesulfonic-5 and acid form 1- or 2-naphthol or l - phenyl-3-methylpyrazolone-5 is subjected, if appropriate in the presence of hydrotropic agents, such as e.g. urea, thiourea, caprolactam and the like and / or surfactants, such as anionic agents, such as sulfosuccinate 1. The method of obtaining chromocomplex dyes of the type 1: 1 of the general formula 1, in which A represents the residue of the general formula 2, in which Rj represents a hydrogen atom or a nitro group, and Y represents a hydrogen, sodium, potassium atom or an ammonium or ammonium group or A represents a residue of general formula 3, where R? is a hydrogen or chlorine atom or a nitro group, B is a residue of formula 4, 5 or 6, and X is a Cl, SO4, H5D4- or HCOO anion by coupling 1-azo-2-oxynaphthalenesulfonic acid-4,1 -azo-2-oxy-6-nitronaphthalenesulfonic-4,1-azo-2-oxybenzenesulfonic-5,1-azo-2-oxy-5-nitrobenzenesulfonic-3,1-azo-2-oxy-5-chlorobenzenesulfonic-3 , 1-azo-2-oxy-3-nitrobenzenesulfonic-5 or 1-azo-2-oxy-3-chlorobenzenesulfonic-5 with 1- or 2-naphthol or with 1-phenyl-3-methylpyrazolone-5 in an aqueous medium and chromating the resulting monoazo dye of the general formula HA-N = N-BH, in which the symbols have the above meanings, in an acidic aqueous medium at a pH below 3, with a trivalent chromium salt used in an amount not less than 1 gram atom of chromium per 1 mole of monoazo dye, characterized in that the mixture containing suspensions of 1-azo-2-oxy-naphthalenesulfonic-4,1-azo-2-oxy-6-nitronaphthalenesulfonic acid-4,1-azo-2-oxybenzenesulfonic-5,1-azo 2-o xy-5-nitrobenzenesulfonic-3,1-azo-2-oxy-5-chlorobenzenesulfonic-3,1-azo-2-oxy-3-nitrobenzenesulfonic-5 or 1-azo-2-oxy-3-chlorobenzenesulfonic-5 and the acidic form of 1- or 2-naphthol or 1-phenyl-3-methylpyrazolone-5 is subjected, if appropriate, in the presence of hydrotropes, e.g. urea, thiourea, kaorolactam and the like, and / or surfactants, such as anionic agents, such as e.g. 2-ethylhexyl sulphosuccinate or sodium salt of condensed polynuclear aromatic sulphonic acids, cationic agents, e.g. triethanolamine stearic acid ester or non-ionic agents, e.g. or mixtures of these agents, such as, for example, the composition of the condensation product of caprolactam with triethanolamine and ethoxylated alkylphenol, pretreatment with stirring at a pH below 2, followed by the gradual alkalisation of the p The coupling reaction is carried out at pH 4-11, and the obtained monoazo dye, having the general formula HA-N = N-BH, is subjected, optionally after its separation from the coupling reaction medium, to chrome plating with a trivalent chromium salt at a pH below 3. 2. A method for obtaining chromocomplex dyes of the type 1: 1 p of the general formula I, in which A is Rj representing the general formula II, in which Rj is a hydrogen atom or a nitro group, and Y is a hydrogen, sodium, potassium or ammonium atom or A represents a residue of the general formula 3, wherein R 5 is a hydrogen or chlorine atom or a nitro group, B is a residue of the formula 4, 5 or 6, and X is an anion Cl ", SO 4, HSO 4" or HCOO ", on by coupling kwa 153 577 su 1-azo-2-oxy-naphthalenesulfonic-4,1-azo-2-oxy-6-nitronaphthalenesulfonic-4,1-azo-2-oxybenzenesulfonic-5,1-azo-2-oxy-5-nitrobenzenesulfonic-3 , 1-azo-2-oxy-5-chlorobenzenesulfonic-3,1-azo-2-oxy-3-nitrobenzenesulfonic-5 or 1-azo-2-oxy-3-chlorobenzenesulfonic-5 with 1- or 2-naphthol or 1-phenyl-3-methylpyrazolone-5 in an aqueous medium and the chromation of the resulting monoazo dye of the general formula HA-N = N-BH, in which the symbols have the above meanings, in an acidic aqueous medium at a pH below 3, with a trivalent chromium salt , used in an amount of not less than 1 gram of chromium atoms per 1 mole of monoazo dye, characterized in that the mixture containing acid suspensions 2-ethylhexyl or sodium salt of condensed polynuclear aromatic sulfonic acids, cationic agents, such as triethanolamine stearic acid ester or nonionic agents, such as, for example, polycondensation products of ethylene oxide or condensation products of ethylene oxide with phenol derivatives or oleyl alcohol derivatives, may be mixtures of these agents, e.g. the composition of the condensation product of caprolactam with triethanolamine and ethoxylated alkylphenol, pretreatment by stirring at a pH below 2, after which the medium is gradually alkalinized and the coupling reaction is carried out at pH 4-11, and the obtained monoazo dye having the general formula HA-N = N-BH is optionally, after its separation from the coupling reaction medium, subjected to chrome plating with a trivalent chromium salt, the chromating reaction starting at pH 3-9, and the resulting 1: 2 chromocomplex dye mixture of general formula 7, in which the symbols they have the meanings given above and the chro salts The trivalent mu-dye and optionally the monoazo dye of formula HA-N = N-BH and the chromo complex dye type 1: 1 are further treated with the trivalent chromium salt contained in the mixture at a pH below 3. + a: hk b • o N k to k a N k U Publishing House? 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