CN105504868B - Red reactive dye - Google Patents

Red reactive dye Download PDF

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CN105504868B
CN105504868B CN201510875721.1A CN201510875721A CN105504868B CN 105504868 B CN105504868 B CN 105504868B CN 201510875721 A CN201510875721 A CN 201510875721A CN 105504868 B CN105504868 B CN 105504868B
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condensation
solution
structural formula
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CN105504868A (en
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张兴华
李荣才
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Tianjin Dek Chemical Co Ltd
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Tianjin Dek Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
    • C09B62/503—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring the reactive group being an esterified or non-esterified hydroxyalkyl sulfonyl or mercaptoalkyl sulfonyl group, a quaternised or non-quaternised aminoalkyl sulfonyl group, a heterylmercapto alkyl sulfonyl group, a vinyl sulfonyl or a substituted vinyl sulfonyl group, or a thiophene-dioxide group
    • C09B62/507—Azo dyes
    • C09B62/51—Monoazo dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
    • C09B62/04—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a triazine ring
    • C09B62/043—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a triazine ring containing two or more triazine rings linked together by a non-chromophoric link
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
    • C09B62/04—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a triazine ring
    • C09B62/08—Azo dyes
    • C09B62/085—Monoazo dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/38—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes
    • D06P1/382—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes reactive group directly attached to heterocyclic group
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/38—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes
    • D06P1/384—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes reactive group not directly attached to heterocyclic group
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/008—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated using reactive dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/30—Ink jet printing

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  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Coloring (AREA)

Abstract

The invention relates to a red reactive dye, which has a structural general formula shown in a formula (I):

Description

Red reactive dye
Technical Field
The invention belongs to the field of reactive dyes, and particularly relates to a red reactive dye and a preparation method thereof.
Background
The reactive dye is more and more widely applied to the printing and dyeing process due to the bright color, convenient application, covalent bond combination with fiber and excellent fastness performance. With the development of application performance, the dyeing of the reactive dye is spread to the dyeing of cotton, wool, hemp, nylon, silk and other fiber fabrics, and the application range is wider and wider. The invention aims to provide a red reactive dye which has excellent water solubility, high dyeing rate and wet processing fastness of wet rubbing resistance, is one of the main hues of the dye, and is the dye with the largest dyeing dosage for the current cellulose fibers. The dyeing method is suitable for pure cotton dyeing and is suitable for digital ink-jet printing pure cotton dyeing.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: provides a novel reactive group reactive dye which is not easy to hydrolyze in aqueous solution and has excellent water solubility, high dyeing rate and wet rubbing resistance.
The technical scheme adopted by the invention is as follows:
a red reactive dye has a general structural formula of formula (I):
wherein R1 is any substituent of the following structural formula (1-1) to structural formula (1-6):
Figure BDA0000865625790000012
Figure BDA0000865625790000021
wherein R2 is any substituent of the following structural formula (2-1) to structural formula (2-3):
m is H or an alkali metal. Preferably, M is-H or-Na or-K.
Preferably, R1 is a substituent of structural formula (1-5) or structural formula (1-6).
Preferably, R2 is a substituent of formula (2-3).
The present invention also provides a process for the preparation of a compound of formula (I) above, comprising the steps of:
firstly, a condensation reaction:
adding sodium bicarbonate (NaHCO) to any compound of the following formula3Solution), adding ice, cyanuric chloride and ice grinding cyanuric chloride into a reaction kettle for five minutes, dropwise adding the dissolved solution shown in the following formula, controlling the temperature T to be 0-10 ℃ and the pH to be 2.0-4.5 in the condensation process, reacting for 3-5 hours, performing liquid chromatography analysis, obtaining a condensate in one step after the condensate is qualified, and performing the next step of reaction.
Figure BDA0000865625790000041
II, carrying out secondary condensation reaction:
adding the dissolved ethylenediamine into the one-step condensation product, heating, and adding sodium carbonate (Na)2CO3Solution) to control the pH value of the reaction product and the temperature T is 30-45 deg.C during condensationReacting for 4-6 hours at pH 6.0-8.0, and controlling the reaction end point by liquid chromatography; obtaining a second-step condensation compound, and cooling the condensation compound to be subjected to the next reaction;
and thirdly, carrying out a tertiary condensation reaction:
adding ice, cyanuric chloride and ice grinding cyanuric chloride into a reaction kettle for five minutes, then dropwise adding the two-step condensation compound into the reaction kettle, controlling the temperature T to be 0-10 ℃ and the pH to be 3.0-5.0 in the condensation process, reacting for 3-5 hours, analyzing by liquid chromatography, obtaining the three-step condensation compound after the condensation compound is qualified, and cooling to carry out the next reaction.
Fourthly, carrying out a four-condensation reaction:
adding H acid dry powder into the condensate obtained in the three steps, heating, controlling the pH value of reactants by using soda ash to ensure that the reactants react for 4 to 6 hours in the condensation process under the condition that the temperature T is 30 to 45 ℃ and the pH value is 5.0 to 7.0, and controlling the reaction end point by using liquid chromatography. And cooling to obtain a condensation compound for the next reaction.
Fifthly, diazotization reaction:
dissolving any compound in the following structural formula by using baking soda or caustic soda flakes (NaOH solution), then adding hydrochloric acid, adding ice, rapidly adding sodium nitrite solution to carry out diazotization reaction, keeping the starch potassium iodide test paper blue at the temperature of 0-5 ℃ in the diazotization reaction process, and obtaining the diazonium salt after the reaction is finished.
Figure BDA0000865625790000061
Sixthly, coupling reaction
Slowly dropwise adding the diazonium salt obtained in the fifth step into the four-step condensation compound obtained in the fourth step, adjusting the pH value of the solution to 6.0-8.0 by using 15% sodium carbonate solution in the dropwise adding process, and reacting for 2.0-3.0 hours until the reaction time is up to standard, thus obtaining the dye solution with the structural formula (I).
Preferably, the method further comprises the steps of:
seventhly, refining
Adjusting the acid of the synthesized dye, adding salt for salting out, filtering to obtain a filter cake, enabling the solid content of the filter cake of the dye to reach more than 40%, dissolving the filter cake of the dye in a pollution-free stainless steel tank, and filtering to obtain a dye solution.
Eighthly, carrying out post-treatment desalting:
the dye solution is desalted through a semipermeable membrane. After the salt is removed, a preservative, a pH value regulator, a bactericide, a viscosity regulator and a hydrolysis-preventing assistant are added. And packaging the finished product after the detection is qualified.
The invention has the following beneficial effects:
the dye disclosed by the invention can be suitable for dyeing cellulose fibers and protein fibers, is suitable for dyeing nylon fibers after hydrolysis, and is more suitable for dyeing pure cotton in digital ink-jet printing.
The red reactive dye has excellent water solubility, high dyeing rate and wet processing fastness of wet friction resistance on digital ink-jet printing, and no wastewater discharge in the printing and dyeing process.
Detailed Description
In order to understand the present invention, the following examples are given to further illustrate the present invention, but not to limit the present invention.
Example 1
A red reactive dye having the formula (ii):
the preparation method of the dye comprises the following steps:
firstly, one-step condensation reaction: adding 4500L of bottom water into a 10-ton tank, using baking soda to adjust 242KG of o-carboxyaniline m-sulfonic acid into a solution to ensure that the pH of the solution is 5.0-7.0, adding 4000L of bottom water into a 35-ton tank, adding 3 ton of ice, adding 605KG of cyanuric chloride into the 35-ton reaction tank, stirring, dropwise adding the o-carboxyaniline m-sulfonic acid solution into the 35-ton reaction tank, using a soda solution to control the pH of one-step condensation reaction to be 3.0-4.5 in the dropwise adding process, controlling the temperature to be 0-10 ℃ in the dropwise adding process, reacting for 3-5 hours after the dropwise adding is finished, performing liquid chromatography analysis, obtaining a one-step condensation product after the product is qualified, and performing two-step condensation reaction.
Two-step condensation reaction
Directly adding an ethylenediamine solution 195KG into the one-step condensation product obtained in the first step, controlling the pH of a reactant to be 6.0-8.0 by using a soda solution after adding, heating to a temperature T of 30-40 ℃, reacting for 5 hours, obtaining a two-step condensation product after the liquid chromatography is qualified, cooling to 10-15 ℃, and carrying out a three-condensation reaction;
three, three-step condensation reaction:
1000L of bottom water is added into a 35-ton tank, 1500 tons of ice are added, and cyanuric chloride 605KG is milled for 5 minutes by the ice mill. Adding the mixture into a 35-ton reaction tank, stirring, dropwise adding a two-step condensation compound, controlling the pH value of a reactant to be 3.0-5.0 by using a sodium carbonate solution after adding, controlling the temperature to be 0-10 ℃ in the reaction process, and waiting for a tetra-condensation reaction after the liquid chromatography is qualified;
four-step condensation reaction:
directly adding 1261KG H acid dry powder into the three-step condensation compound of the three-step condensation reaction, controlling the pH of the reactant to be 5.0-7.0 by using a soda solution after the H acid dry powder is added, continuously keeping the temperature T to be 30-40 ℃, reacting for 4 hours, and obtaining the four-step condensation compound after the liquid chromatography is qualified, wherein the condensation compound is subjected to a coupling reaction;
fifthly, diazotization reaction:
adding 4000L of bottom water into a 10-ton tank, then adding 481KG of 3-beta- (sulfuric ester ethyl sulfonyl) aniline-5-sulfonic acid, adding hydrochloric acid, adding 2 tons of ice, uniformly stirring and rapidly adding a sodium nitrite solution, checking by using a potassium starch iodide test paper in the diazotization process to keep the potassium starch iodide test paper blue, controlling the temperature to be 0-5 ℃, reacting for 3 hours, and then removing excessive nitrous acid by using sulfamic acid to obtain diazonium salt to be subjected to coupling reaction.
Sixthly, coupling reaction:
slowly dropwise adding the diazonium salt obtained in the fifth step into the four-step condensation compound obtained in the fourth step, adjusting the pH of the solution to 6.0-8.0 by using 15% sodium carbonate solution in the dropwise adding process, and reacting for 2.0-3.0 hours until the reaction time is up to standard, thus obtaining the dye solution with the structural formula (II).
Seventhly, post-treatment and salting out:
after the reaction is finished, directly mixing and spraying or salting out according to the printing and dyeing requirements, for example, adding sodium chloride with the volume of 20% for salting out, carrying out pressure filtration after salting out for 2 hours to obtain a filter cake, and weighing.
Eighthly, membrane treatment:
the dye solution is desalted through a semipermeable membrane. After the salt is removed, a preservative, a pH value regulator, a bactericide, a viscosity regulator and a hydrolysis-preventing assistant are added. And packaging after the detection is qualified.
The application properties of the red reactive dye prepared in example 1 are shown in the following table:
Figure BDA0000865625790000081
example 2
A red reactive dye has a structural formula as follows:
Figure BDA0000865625790000082
wherein R1 is:
r2 is:
Figure BDA0000865625790000091
m is Na.
The preparation method of the dye comprises the following steps:
firstly, one-step condensation reaction: adding 4500L of bottom water into a 10-ton tank, using baking soda to adjust 3-beta- (sulfuric ester ethyl sulfuryl) aniline-5-sulfonic acid 1713KG into a solution to enable the pH of the solution to be 5.0-7.0, adding 4000L of bottom water into a 35-ton tank, adding 3 tons of ice, adding cyanuric chloride 605KG into a 35-ton reaction tank, carrying out ice grinding and stirring, dropwise adding 3-beta- (sulfuric ester ethyl sulfuryl) aniline-5-sulfonic acid solution into the 35-ton reaction tank, using a soda solution to control the pH of one-step condensation reaction to be 3.0-4.5 in the dropwise adding process, controlling the temperature to be 0-10 ℃ in the dropwise adding process, reacting for 3-5 hours after the dropwise adding is finished, carrying out liquid chromatography analysis, obtaining a one-step condensation product after the solution is qualified, and carrying out two-step condensation reaction.
Two-step condensation reaction
Directly adding an ethylenediamine solution 195KG into the one-step condensation product obtained in the first step, controlling the pH of a reactant to be 6.0-8.0 by using a soda solution after adding, heating to a temperature T of 30-40 ℃, reacting for 5 hours, obtaining a two-step condensation product after the liquid chromatography is qualified, cooling to 10-15 ℃, and carrying out a three-condensation reaction;
three, three-step condensation reaction:
adding bottom water and 1500KG ice into a 35-ton tank, adding 600KG cyanuric chloride into a 35-ton reaction tank, stirring by an ice mill, dropwise adding a two-step condensation compound, and controlling the pH of a reactant to be 3.0-5.0 by using a sodium carbonate solution after adding, wherein the temperature is controlled to be 0-10 ℃ in the reaction process, and after the liquid chromatography is qualified, carrying out a four-condensation reaction;
four-step condensation reaction:
directly adding 1258KG H acid dry powder into the three-step condensation product of the three-step condensation reaction, controlling the pH of the reactant to be 5.0-7.0 by using a soda solution after the addition, continuously keeping the temperature T to be 30-40 ℃, reacting for 4 hours, and obtaining a four-step condensation product after the liquid chromatography is qualified, wherein the condensation product is subjected to a coupling reaction;
preparation of the pentadiazonium salt:
1) one-step condensation reaction: adding 4500L of bottom water into a 10-ton tank, using baking soda to adjust 1700KG of 3-beta- (sulfuric ester ethyl sulfuryl) aniline-5-sulfonic acid into a solution to enable the pH of the solution to be 5.0-7.0, adding 4000L of bottom water into a 35-ton tank, adding 3 tons of ice, adding 598KG of cyanuric chloride into a 35-ton reaction tank, stirring by an ice mill, dropwise adding 3-beta- (sulfuric ester ethyl sulfuryl) aniline-5-sulfonic acid solution into the 35-ton reaction tank, controlling the pH of one-step condensation reaction to be 3.0-4.5 by using a soda solution in the dropwise adding process, controlling the temperature to be 0-10 ℃ in the dropwise adding process, reacting for 3-5 hours after the dropwise adding is finished, performing liquid chromatography analysis, obtaining a one-step condensation compound after the qualified reaction, and performing two-step condensation reaction.
2) Two-step condensation reaction
Directly adding 806KG 2, 4-diaminobenzene sulfonic acid sodium into the condensate obtained in the step 1), controlling the pH of the reactant to be 6.0-8.0 by using a soda solution after adding, heating to the temperature T of 30-40 ℃, reacting for 5 hours, obtaining a two-step condensate after the liquid chromatography is qualified, cooling to the temperature of 10-15 ℃, and waiting for diazotization reaction.
3) Adding hydrochloric acid into the condensation reaction in the step 2), adding 2 tons of ice, stirring uniformly and quickly adding a sodium nitrite solution, checking by using a potassium starch iodide test paper in the diazotization process to keep the potassium starch iodide test paper blue, controlling the temperature to be 0-5 ℃, reacting for 3 hours, then removing excessive nitrous acid by using sulfamic acid to obtain diazonium salt, and waiting for coupling reaction.
Sixthly, coupling reaction:
slowly dropwise adding the diazonium salt obtained in the fifth step into the four-step condensation compound obtained in the fourth step, adjusting the pH of the solution to 6.0-8.0 by using 15% sodium carbonate solution in the dropwise adding process, and reacting for 2.0-3.0 hours until the solution is qualified, thus obtaining the dye solution.
Seventhly, post-treatment and salting out:
after the reaction is finished, directly mixing and spraying or salting out according to the printing and dyeing requirements, for example, adding sodium chloride with the volume of 20% for salting out, carrying out pressure filtration after salting out for 2 hours to obtain a filter cake, and weighing.
Eighthly, membrane treatment:
the dye solution is desalted through a semipermeable membrane. After the salt is removed, a preservative, a pH value regulator, a bactericide, a viscosity regulator and a hydrolysis-preventing assistant are added. And packaging after the detection is qualified.
The application properties of the red reactive dye prepared in example 2 are shown in the following table:
example 3
A red reactive dye has a structural formula as follows:
Figure BDA0000865625790000111
wherein R1 is:
r2 is:
Figure BDA0000865625790000113
m is Na.
The preparation method of the dye comprises the following steps:
one-step condensation reaction: adding 4500L of bottom water into a 10-ton tank, using baking soda to adjust 3-beta- (sulfuric ester ethyl sulfuryl) aniline-5-sulfonic acid 1713KG into a solution to enable the pH of the solution to be 5.0-7.0, adding 4000L of bottom water into a 35-ton tank, adding 3 tons of ice, adding cyanuric chloride 605KG into a 35-ton reaction tank, carrying out ice grinding and stirring, dropwise adding 3-beta- (sulfuric ester ethyl sulfuryl) aniline-5-sulfonic acid solution into the 35-ton reaction tank, using a soda solution to control the pH of one-step condensation reaction to be 3.0-4.5 in the dropwise adding process, controlling the temperature to be 0-10 ℃ in the dropwise adding process, reacting for 3-5 hours after the dropwise adding is finished, carrying out liquid chromatography analysis, obtaining a one-step condensation product after the solution is qualified, and carrying out two-step condensation reaction.
Two-step condensation reaction
Directly adding an ethylenediamine solution 195KG into the one-step condensation product obtained in the first step, controlling the pH of a reactant to be 6.0-8.0 by using a soda solution after adding, heating to a temperature T of 30-40 ℃, reacting for 5 hours, obtaining a two-step condensation product after the liquid chromatography is qualified, cooling to 10-15 ℃, and carrying out a three-condensation reaction;
three, three-step condensation reaction:
adding bottom water and 1500KG ice into a 35-ton tank, adding 600KG cyanuric chloride into a 35-ton reaction tank, stirring by an ice mill, dropwise adding a two-step condensation compound, and controlling the pH of a reactant to be 3.0-5.0 by using a sodium carbonate solution after adding, wherein the temperature is controlled to be 0-10 ℃ in the reaction process, and after the liquid chromatography is qualified, carrying out a four-condensation reaction;
four-step condensation reaction:
directly adding 1280KG of H acid dry powder into the three-step condensation compound of the three-step condensation reaction, controlling the pH of the reactant to be 5.0-7.0 by using a soda solution after adding, continuously keeping the temperature T to be 30-40 ℃, reacting for 4 hours, and obtaining the four-step condensation compound after the liquid chromatography is qualified, wherein the four-step condensation compound is obtained after the coupling reaction;
and (3) carrying out a quintuple nitriding reaction:
adding 4000L of bottom water into a 10-ton tank, then adding 697KG of 6-beta- (sulfuric ester ethyl sulfonyl) -2-aminonaphthalene sulfonic acid, adding hydrochloric acid, adding 2 tons of ice, uniformly stirring and rapidly adding a sodium nitrite solution, checking by using a potassium starch iodide test paper in the diazotization process to keep the potassium starch iodide test paper blue, controlling the temperature to be 0-5 ℃, reacting for 3 hours, and then removing excessive nitrous acid by using sulfamic acid to obtain diazonium salt to be subjected to coupling reaction.
Sixthly, coupling reaction:
slowly dropwise adding the diazonium salt obtained in the fifth step into the four-step condensation compound obtained in the fourth step, adjusting the pH of the solution to 6.0-8.0 by using 15% sodium carbonate solution in the dropwise adding process, and reacting for 2.0-3.0 hours until the solution is qualified, thus obtaining the dye solution.
Seventhly, post-treatment and salting out:
after the reaction is finished, directly mixing and spraying or salting out according to the printing and dyeing requirements, for example, adding sodium chloride with the volume of 20% for salting out, carrying out pressure filtration after salting out for 2 hours to obtain a filter cake, and weighing.
Eighthly, membrane treatment:
the dye solution is desalted through a semipermeable membrane. After the salt is removed, a preservative, a pH value regulator, a bactericide, a viscosity regulator and a hydrolysis-preventing assistant are added. And packaging after the detection is qualified.
The application properties of the red reactive dye prepared in example 3 are shown below:
example 4
A red reactive dye has a structural formula as follows:
Figure BDA0000865625790000131
the preparation method of the dye comprises the following steps:
one-step condensation reaction: adding 2500L of bottom water into a 10-ton tank, using baking soda to adjust 742KG of m-aminobenzene sulfonic acid into a solution to enable the pH of the solution to be 5.0-7.0, adding 4000L of bottom water into a 35-ton tank, adding 3 tons of ice, adding 605KG of cyanuric chloride into the 35-ton reaction tank, carrying out ice grinding and stirring, dropwise adding the m-aminobenzene sulfonic acid solution into the 35-ton reaction tank, using a soda solution to control the pH of one-step condensation reaction to be 3.0-4.5 in the dropwise adding process, controlling the temperature to be 0-10 ℃ in the dropwise adding process, reacting for 3-5 hours, carrying out liquid chromatography analysis, obtaining a one-step condensation compound after the condensation compound is qualified, and waiting for a two-step condensation reaction.
Two-step condensation reaction
Directly adding an ethylenediamine solution 195KG into the one-step condensation product obtained in the first step, controlling the pH of a reactant to be 6.0-8.0 by using a soda solution after adding, heating to a temperature T of 30-40 ℃, reacting for 5 hours, obtaining a two-step condensation product after the liquid chromatography is qualified, cooling to 10-15 ℃, and carrying out a three-condensation reaction;
three, three-step condensation reaction:
adding bottom water and 1500KG ice into a 35-ton tank, adding 600KG cyanuric chloride into a 35-ton reaction tank, stirring by an ice mill, dropwise adding a two-step condensation compound, and controlling the pH of a reactant to be 3.0-5.0 by using a sodium carbonate solution after adding, wherein the temperature is controlled to be 0-10 ℃ in the reaction process, and after the liquid chromatography is qualified, carrying out a four-condensation reaction;
four-step condensation reaction:
directly adding 1270KG of H acid dry powder into the three-step condensation compound of the three-step condensation reaction, controlling the pH of the reactant to be 5.0-7.0 by using a soda solution after the H acid dry powder is added, continuously keeping the temperature T to be 30-40 ℃, reacting for 4 hours, and obtaining a four-step condensation compound after the liquid chromatography is qualified, wherein the condensation compound is subjected to a coupling reaction;
and (3) carrying out a quintuple nitriding reaction:
adding 4000L of bottom water into a 10-ton tank, then adding 1180KG of 2-naphthylamine-4, 8-disulfonic acid, adding hydrochloric acid, adding 2 tons of ice, uniformly stirring and quickly adding a sodium nitrite solution, using a potassium starch iodide test paper to check and maintain the potassium starch iodide test paper to be blue in the diazotization process, controlling the temperature to be 0-5 ℃, reacting for 3 hours, and then using sulfamic acid to remove excessive nitrous acid to obtain diazonium salt to be subjected to coupling reaction.
Sixthly, coupling reaction:
slowly dropwise adding the diazonium salt obtained in the fifth step into the four-step condensation compound obtained in the fourth step, adjusting the pH of the solution to 6.0-8.0 by using 15% sodium carbonate solution in the dropwise adding process, and reacting for 2.0-3.0 hours until the solution is qualified, thus obtaining the dye solution.
Seventhly, post-treatment and salting out:
after the reaction is finished, directly mixing and spraying or salting out according to the printing and dyeing requirements, for example, adding sodium chloride with the volume of 20% for salting out, carrying out pressure filtration after salting out for 2 hours to obtain a filter cake, and weighing.
Eighthly, membrane treatment:
the dye solution is desalted through a semipermeable membrane. After the salt is removed, a preservative, a pH value regulator, a bactericide, a viscosity regulator and a hydrolysis-preventing assistant are added. And packaging after the detection is qualified.
The application properties of the red reactive dye prepared in example 4 are shown below:
Figure BDA0000865625790000141
the method of the present invention has been described by way of specific examples. The invention can be used for other purposes by those skilled in the art by appropriately changing the raw materials, the process conditions and the like without departing from the content of the invention, and all similar substitutes and modifications obvious to those skilled in the art are deemed to be included in the scope of the invention.

Claims (5)

1. A red reactive dye, characterized in that: the red reactive dye has a structural general formula shown in a formula (I):
Figure FDA0002161894180000011
wherein R1 is any substituent of the following structural formula (1-1) to structural formula (1-6):
Figure FDA0002161894180000012
Figure FDA0002161894180000021
wherein R2 is any substituent of the following structural formula (2-1) to structural formula (2-3):
m is H or an alkali metal.
2. A red reactive dye according to claim 1, wherein: and M is-H or-Na or-K.
3. A red reactive dye according to claim 1, wherein: and R1 is a substituent of a structural formula (1-5) or a structural formula (1-6).
4. A red reactive dye according to any one of claims 1 to 3, wherein: and R2 is a substituent of a structural formula (2-3).
5. A process for the preparation of a red reactive dye according to any one of claims 1 to 4, characterized in that: the method comprises the following steps: firstly, a condensation reaction:
using NaHCO to react with any compound in the following structural formula3Dissolving the solution, namely adding ice, cyanuric chloride and ice-grinding cyanuric chloride into a reaction kettle for five minutes, dropwise adding the dissolved solution shown as the following formula, controlling the temperature T to be 0-10 ℃ and the pH to be 2.0-4.5 in the condensation process, reacting for 3-5 hours, carrying out liquid chromatography analysis, obtaining a condensate in one step after the condensate is qualified, and carrying out the next step of reaction;
Figure FDA0002161894180000031
3-beta- (sulfuric ester ethyl sulfuryl) aniline-5-sulfonic acid
Figure FDA0002161894180000032
O-carboxyaniline meta-sulfonic acid
Figure FDA0002161894180000033
3-sulfonic acid aniline
II, carrying out secondary condensation reaction:
adding the dissolved ethylenediamine into the one-step condensation product, heating, and adding Na2CO3Controlling the pH value of the condensation reactant by the solution, controlling the temperature T to be 30-45 ℃ and the pH to be 6.0-8.0 in the condensation process, reacting for 4-6 hours, and controlling the reaction end point by liquid chromatography; obtaining a second-step condensation compound, and cooling the condensation compound to be subjected to the next reaction;
and thirdly, carrying out a tertiary condensation reaction:
adding ice, cyanuric chloride and ice grinding cyanuric chloride into a reaction kettle for five minutes, dropwise adding the two-step condensation compound into the reaction kettle, controlling the temperature T to be 0-10 ℃ and the pH to be 3.0-5.0 in the condensation process, reacting for 3-5 hours, analyzing by liquid chromatography, obtaining the three-step condensation compound after the condensation compound is qualified, and cooling to carry out the next reaction;
fourthly, carrying out a four-condensation reaction:
adding H acid dry powder into the condensate obtained in the three steps, heating, controlling the pH value of reactants by using soda ash to ensure that the reactants react for 4 to 6 hours in the condensation process under the condition that the temperature T is 30 to 45 ℃ and the pH value is 5.0 to 7.0, and controlling the reaction end point by using liquid chromatography; obtaining a condensation compound, cooling and carrying out the next reaction;
fifthly, diazotization reaction:
dissolving any compound in the following structural formula by using baking soda or NaOH solution, then adding hydrochloric acid, adding ice, quickly adding sodium nitrite solution to carry out diazotization reaction, keeping the starch potassium iodide test paper blue at the temperature of 0-5 ℃ in the diazotization reaction process, and obtaining diazonium salt after the reaction is finished;
Figure FDA0002161894180000041
2-naphthylamine-1-sulfonic acid
Figure FDA0002161894180000042
2-naphthylamine-1, 5-disulfonic acid
Figure FDA0002161894180000043
2-amino-6-beta- (sulfatoethylsulfonyl) naphthalenesulfonic acid
Figure FDA0002161894180000044
2-naphthylamine-4, 8-disulfonic acid
3-beta- (sulfuric ester ethyl sulfuryl) aniline-5-sulfonic acid
Sixthly, coupling reaction
Slowly dropwise adding the diazonium salt obtained in the fifth step into the four-step condensation compound obtained in the fourth step, adjusting the pH value of the solution to 6.0-8.0 by using 15% sodium carbonate solution in the dropwise adding process, and reacting for 2.0-3.0 hours until the reaction time is up to standard, thus obtaining the dye solution with the structural formula (I).
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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001214087A (en) * 2000-02-04 2001-08-07 Sumitomo Chem Co Ltd Reactive dye composition and dyeing method using the same
CN102391683A (en) * 2011-09-29 2012-03-28 丽源(湖北)科技有限公司 Bright red azo dye mixture and use thereof
CN102504583A (en) * 2011-09-29 2012-06-20 丽源(湖北)科技有限公司 Scarlet azo dye and its preparation and application
CN102876071A (en) * 2012-09-20 2013-01-16 天津德凯化工股份有限公司 Red reactive dye and preparation method thereof
CN103554981A (en) * 2013-09-29 2014-02-05 天津德凯化工股份有限公司 Red reactive dye
CN103554976A (en) * 2013-09-29 2014-02-05 天津德凯化工股份有限公司 Red reactive dye and preparation method thereof
CN103554979A (en) * 2013-09-29 2014-02-05 天津德凯化工股份有限公司 Active red dye and preparation method thereof
CN103554980A (en) * 2013-09-29 2014-02-05 天津德凯化工股份有限公司 Red reactive dye and preparation method thereof
CN104312201A (en) * 2014-09-28 2015-01-28 天津德凯化工股份有限公司 Red reactive dye for nylon

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001214087A (en) * 2000-02-04 2001-08-07 Sumitomo Chem Co Ltd Reactive dye composition and dyeing method using the same
CN102391683A (en) * 2011-09-29 2012-03-28 丽源(湖北)科技有限公司 Bright red azo dye mixture and use thereof
CN102504583A (en) * 2011-09-29 2012-06-20 丽源(湖北)科技有限公司 Scarlet azo dye and its preparation and application
CN102876071A (en) * 2012-09-20 2013-01-16 天津德凯化工股份有限公司 Red reactive dye and preparation method thereof
CN103554981A (en) * 2013-09-29 2014-02-05 天津德凯化工股份有限公司 Red reactive dye
CN103554976A (en) * 2013-09-29 2014-02-05 天津德凯化工股份有限公司 Red reactive dye and preparation method thereof
CN103554979A (en) * 2013-09-29 2014-02-05 天津德凯化工股份有限公司 Active red dye and preparation method thereof
CN103554980A (en) * 2013-09-29 2014-02-05 天津德凯化工股份有限公司 Red reactive dye and preparation method thereof
CN104312201A (en) * 2014-09-28 2015-01-28 天津德凯化工股份有限公司 Red reactive dye for nylon

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