CN112480708A - Reactive dye red and preparation method and application thereof - Google Patents

Reactive dye red and preparation method and application thereof Download PDF

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Publication number
CN112480708A
CN112480708A CN202011152683.4A CN202011152683A CN112480708A CN 112480708 A CN112480708 A CN 112480708A CN 202011152683 A CN202011152683 A CN 202011152683A CN 112480708 A CN112480708 A CN 112480708A
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formula
compound shown
reactive dye
reaction
independently selected
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CN112480708B (en
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陆再宏
陆海英
王高峰
庄磊
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Suzhou Aoyuansheng New Material Technology Co ltd
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Suzhou Aoyuansheng New Material Technology 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
    • C09B62/513—Disazo or polyazo dyes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • 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
    • C09B62/09—Disazo or polyazo 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
    • D06P3/58—Material containing hydroxyl groups
    • D06P3/60—Natural or regenerated cellulose
    • D06P3/66—Natural or regenerated cellulose using reactive dyes
    • D06P3/663—Natural or regenerated cellulose 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
    • 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
    • D06P3/58—Material containing hydroxyl groups
    • D06P3/60—Natural or regenerated cellulose
    • D06P3/66—Natural or regenerated cellulose using reactive dyes
    • D06P3/666—Natural or regenerated cellulose using reactive dyes reactive group not directly attached to heterocyclic group

Abstract

The invention relates to a reactive dye red and a preparation method and application thereof, wherein the structure of the reactive dye red is shown as a general formula (I):

Description

Reactive dye red and preparation method and application thereof
Technical Field
The invention belongs to the technical field of dyes, and particularly relates to a reactive dye red as well as a preparation method and application thereof.
Background
When the polyester-cotton blended fabric on the market is dyed, a common dyeing method is a two-bath method, namely, the fabric is dyed and washed by disperse dye, and then dyed and washed by reactive dye. Although the homochromatism is good and the fastness is high, the working procedure is long, the energy consumption is excessive, the energy conservation and emission reduction and the clean production of printing and dyeing enterprises are not facilitated, and the problems of color spots and cylinder difference can be generated in the production along with the prolonging of the processing time, so that the product quality and the efficiency are influenced.
In order to solve the problems, many factories search for one-bath one-step dyeing of polyester cotton, but the existing reactive dye red still has poor high temperature resistance, can only dye at about 50 ℃, and is not suitable for one-bath one-step dyeing by matching with disperse dyes.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an improved reactive dye red and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a reactive dye red has a compound structure shown as a general formula (I):
Figure BDA0002741656380000011
in the formula:
R1、R2、R3、R4each independently selected from H or an alkali metal cation;
M1、M2、M3、M4each independently selected from X, SO3X is alkyl with 1-5 carbon atoms or alkoxy with 1-5 carbon atoms, and X is H or alkali metal cation;
F1、F2each independently selected from Y, SO3Y、
Figure BDA0002741656380000012
Y is H or alkali metal cation, and m and n are respectively and independently selected from integers between 1 and 5;
A1、A2each independently selected from H or an alkali metal cation.
According to some embodiments of the invention, the alkali metal cation is Na, K or Li.
According to some embodiments of the invention, the M is1、M2、M3、M4Each independently selected from H, SO3H、SO3Na、SO3K、SO3Li、CH3O or CH3。
According to some embodiments of the invention, F1、F2Each independently selected from H, SO3H、SO3Na、SO3K、SO3Li、SO2C2H5、SO2C2H4Na、SO2C2H4K、SO2C2H4Li、SO2C2H4OSO3H、SO2C2H4OSO3Na、SO2C2H4OSO3K or SO2C2H4OSO3Li。
According to some embodiments of the invention, in the formula I, the two NH groups on the phenyl ring in the intermediate position are located in the para-position or meta-position, respectively, of the phenyl ring.
According to some embodiments of aspects of the invention, in the general formula I, the COOA1、COOA2Respectively at ortho, meta or para positions of the N group on the ring. Preferably, the COOA1、COOA2Each being meta to the N group on the ring.
According to some embodiments of the invention, the compound of formula I is one of the compounds represented by the following structural formulae:
Figure BDA0002741656380000021
Figure BDA0002741656380000031
the invention adopts another technical scheme that: a preparation method of reactive dye red comprises the following steps:
(1) carrying out primary condensation reaction on a compound shown as a formula II and a compound shown as a formula III to obtain a condensate;
(2) carrying out diazo reaction on the compound shown in the formula IV under the action of nitrous acid to obtain a first intermediate;
(3) carrying out coupling reaction on the first condensate and the first intermediate to obtain a second intermediate;
(4) carrying out secondary condensation reaction on the second intermediate and a compound shown as a formula V to obtain a secondary condensate;
(5) carrying out tertiary condensation reaction on the secondary condensate and a compound shown as a formula VI to obtain reactive dye red;
Figure BDA0002741656380000032
M1、M2each independently selected from X1、SO3X1An alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, wherein X is1Is H or an alkali metal cation;
f is selected from Y1、SO3Y1、
Figure BDA0002741656380000033
Said Y is1Is H or alkali metal cation, m and n are respectively and independently selected from integers between 1 and 5;
R1、R2are independently selected from H or alkali metal cation;
a is selected from H or an alkali metal cation.
According to some embodiment aspects of the invention, the M1、M2Each independently selected from H, SO3H、SO3Na、SO3K、SO3Li、CH3O or CH3。
According to some embodiment aspects of the invention, F is selected from H, SO3H、SO3Na、SO3K、SO3Li、SO2C2H5、SO2C2H4Na、SO2C2H4K、SO2C2H4Li、SO2C2H4OSO3H、SO2C2H4OSO3Na、SO2C2H4OSO3K or SO2C2H4OSO3Li。
According to some embodiment aspects of the invention, the R is1、R2Each independently selected from H, Na, K or Li. Preferably, said R is1、R2Are respectively and independently selected from H or Na, and are not simultaneously Na.
According to some aspects of this embodiment of the invention, in formula V, there are two NH groups on the phenyl ring2The groups are located in the para or meta position, respectively, of the phenyl ring.
According to some embodiment aspects of the invention, a is selected from H, Na, K or Li.
According to some embodiment aspects of the invention, in formula VI, COOA is ortho, meta or para to the N group on the ring. Preferably, in said formula VI, COOA is meta to the N group on the ring.
According to some embodiments of the present invention, step (1) is performed by: and mixing the compound shown in the formula II and the compound shown in the formula III with water, and stirring at the pH value of 1.5-3.0 and the temperature of 0-15 ℃ for reaction to prepare the first condensate, wherein the feeding molar ratio of the compound shown in the formula II to the compound shown in the formula III is 1: 0.97-1.02.
According to some embodiments of the present invention, step (2) is performed by: mixing the compound shown in the formula IV, hydrochloric acid, nitrite and water, and stirring for reaction at 0-15 ℃ to obtain the first intermediate, wherein the feeding molar ratio of the compound shown in the formula IV, HCl and nitrite ions is 1 (1-2.5) to 1-1.1.
According to some embodiments of the invention, in the step (3), the feeding of the first condensate and the first intermediate is performed according to a feeding molar ratio of the compound represented by the formula III to the compound represented by the formula IV of 1: 0.97-1.01, and the coupling reaction is performed at a pH value of 4.5-7.0 and a temperature of 10-20 ℃.
According to some embodiments of the invention, in the step (4), the feeding molar ratio of the compound represented by the formula V to the compound represented by the formula II is 1: 2.0-2.1, and the secondary condensation reaction is performed at a pH value of 4.5-6.0 and a temperature of 30-45 ℃.
According to some embodiments of the invention, in the step (5), the feeding molar ratio of the compound represented by the formula II to the compound represented by the formula VI is 1: 2.0-3.5, and the three-time condensation reaction is performed at a pH value of 5.0-7.0 and a temperature of 75-90 ℃.
According to some example aspects of the invention, the method of making is embodied by the steps of:
(1) mixing the compound shown in the formula II and the compound shown in the formula III with ice water, adding weak base to adjust the pH value to 1.5-3.0, and then stirring and reacting for 2-4 h at 0-15 ℃ to obtain a first reaction liquid, wherein the weak base is one or more of sodium bicarbonate, potassium bicarbonate and lithium bicarbonate;
(2) mixing the compound shown in the formula IV, hydrochloric acid, sodium nitrite and ice water, and stirring and reacting for 1-3 hours at 0-15 ℃ to obtain a second reaction solution;
(3) mixing the first reaction solution and the second reaction solution, adding weak base to adjust the pH value to 4.5-7.0, and reacting for 4-6 h at 10-20 ℃ to obtain a third reaction solution, wherein the weak base is one or more of sodium bicarbonate, potassium bicarbonate and lithium bicarbonate;
(4) adding the compound shown in the formula V into the third reaction liquid, adding weak base to adjust the pH value to be 4.5-6.0, and reacting for 2-5 hours at the temperature of 30-45 ℃ to obtain a fourth reaction liquid, wherein the weak base is one or more of sodium bicarbonate, potassium bicarbonate and lithium bicarbonate;
(5) adding the compound shown in the formula VI into the fourth reaction liquid, adding a strong base to adjust the pH value to be 5.0-7.0, and reacting at 75-90 ℃ for 6-9 h to obtain a fifth reaction liquid, wherein the strong base is one or more of sodium carbonate, lithium carbonate and potassium carbonate;
(6) and drying the fifth reaction solution to obtain the reactive dye red.
According to yet another technical scheme adopted by the invention, the reactive dye red is applied to pure cotton, rayon, T/R or T/C blended fabrics.
When the reactive dye red is used for dyeing pure cotton (or rayon), the reactive dye red and anhydrous sodium sulphate are dissolved in water, the temperature is increased to 100-130 ℃, and the pure cotton (or rayon) is subjected to heat preservation dyeing, cooling, water washing and soaping.
The addition amount of the reactive dye red and the anhydrous sodium sulphate can be added according to the addition amount of the existing reactive dye and anhydrous sodium sulphate, and the heat preservation is usually 20-60 min. Such as about 40 min.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
the reactive dye has higher reactivity, good color fixing capability and good dyeing capability, and the reactive dye does not need to be added with soda for color fixing during dyeing, so that the use of the soda is avoided. Meanwhile, the reactive dye also has high temperature resistance, can be used in cooperation with a disperse dye, and can simultaneously dye T/R or T/C blended products at a temperature higher than 100 ℃, so that a one-bath dyeing process is realized, the dyeing process is simplified, the dyeing time is shortened, the discharge capacity is greatly reduced, and the labor cost and the energy consumption are reduced.
Detailed Description
In order to make the objects, technical solutions and effects of the present invention clearer and clearer, the present invention is described in further detail below. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The raw materials in the following examples are commercially available. The hydrochloric acid used was 30% strength hydrochloric acid.
Example 1
The reactive dye red provided in this example is prepared by the following method:
(1) will be provided with
Figure BDA0002741656380000051
Adding into crushed ice and water, stirring, and adding
Figure BDA0002741656380000052
Adding sodium bicarbonate to adjust the pH value to 2.0-2.5, reacting for 3.5h at the temperature of 5-10 ℃ to obtain a first mixed solution, wherein,
Figure BDA0002741656380000053
and
Figure BDA0002741656380000054
the feeding molar ratio of (A) to (B) is 1: 0.99;
(2) will be provided with
Figure BDA0002741656380000055
Adding the mixture into water and crushed ice, stirring, keeping the temperature at 0-5 ℃, adding hydrochloric acid, adding sodium nitrite, reacting for 1.5 hours to obtain a second mixed solution, wherein,
Figure BDA0002741656380000056
the feeding molar ratio of HCl to sodium nitrite is 1:1.0: 1.01;
(3) adding the second mixed solution obtained in the step (2) into the first mixed solution obtained in the step (1), adding sodium bicarbonate to adjust the pH value to 5.5-6.0, and reacting at 10-15 ℃ for 5.5 hours to obtain a third mixed solution, wherein the feeding of the first mixed solution and the second mixed solution is carried out according to the proportion
Figure BDA0002741656380000057
And
Figure BDA0002741656380000058
the feeding molar ratio of (1: 0.99);
(4) will be provided with
Figure BDA0002741656380000061
Adding the third mixed solution obtained in the step (3), adding sodium bicarbonate to adjust the pH value to 5.5-6.0, reacting for 2.5h at the temperature of 30-35 ℃ to obtain a fourth mixed solution, wherein,
Figure BDA0002741656380000062
and
Figure BDA0002741656380000063
the feeding molar ratio of (A) to (B) is 1: 2.0;
(5) will be provided with
Figure BDA0002741656380000064
Adding the mixture into the fourth mixed solution obtained in the step (4), adding sodium carbonate to adjust the pH value to 5.5-6.0, reacting at 75-80 ℃ for 6.5h to obtain a fifth mixed solution, wherein,
Figure BDA0002741656380000065
and
Figure BDA0002741656380000066
the feeding molar ratio of (1: 2.5);
(6) and (5) drying the fifth mixed solution obtained in the step (5) to obtain the product, namely the reactive dye red.
The structural formula of the product is as follows:
Figure BDA0002741656380000067
example 2
The reactive dye red provided in this example is prepared by the following method:
(1) will be provided with
Figure BDA0002741656380000068
Adding into crushed ice and water, stirring
Figure BDA0002741656380000069
Adding intoThen adding sodium bicarbonate to adjust the pH value to 2.0-2.5, reacting for 3 hours at the temperature of 5-10 ℃ to obtain a first mixed solution, wherein,
Figure BDA00027416563800000610
and
Figure BDA00027416563800000611
the feeding molar ratio of (A) to (B) is 1: 0.99;
(2) will be provided with
Figure BDA00027416563800000612
Adding the mixture into water and crushed ice, stirring, keeping the temperature at 5-8 ℃, adding hydrochloric acid, and then adding sodium nitrite to react for 1.5 hours to obtain a second mixed solution, wherein
Figure BDA00027416563800000613
The feeding molar ratio of HCl to sodium nitrite is 1:1.0: 1.01;
(3) adding the second mixed solution obtained in the step (2) into the first mixed solution obtained in the step (1), adding sodium bicarbonate to adjust the pH value to 5.5-6.0, and reacting for 5 hours at the temperature of 10-15 ℃ to obtain a third mixed solution, wherein the feeding of the first mixed solution and the second mixed solution is carried out according to the proportion
Figure BDA0002741656380000071
And
Figure BDA0002741656380000072
the feeding molar ratio of (1: 0.99);
(4) will be provided with
Figure BDA0002741656380000073
Adding the third mixed solution obtained in the step (3), adding sodium bicarbonate to adjust the pH value to 5.5-6.0, reacting for 3 hours at the temperature of 30-35 ℃ to obtain a fourth mixed solution, wherein,
Figure BDA0002741656380000074
and
Figure BDA0002741656380000075
the feeding molar ratio of (A) to (B) is 1: 2.0;
(5) will be provided with
Figure BDA0002741656380000076
Adding the mixture into the fourth mixed solution obtained in the step (4), adding sodium carbonate to adjust the pH value to 5.5-6.0, reacting at 75-80 ℃ for 6h to obtain a fifth mixed solution, wherein,
Figure BDA0002741656380000077
and
Figure BDA0002741656380000078
the feeding molar ratio of (1: 2.5);
(6) and (5) drying the fifth mixed solution obtained in the step (5) to obtain the product, namely the reactive dye red.
The structural formula of the product is as follows:
Figure BDA0002741656380000079
example 3
The reactive dye red provided in this example is prepared by the following method:
(1) will be provided with
Figure BDA00027416563800000710
Adding into crushed ice and water, stirring, and adding
Figure BDA00027416563800000711
Adding sodium bicarbonate to adjust the pH value to 2.0-2.5, reacting for 4 hours at the temperature of 5-10 ℃ to obtain a first mixed solution, wherein,
Figure BDA00027416563800000712
and
Figure BDA00027416563800000713
the feeding molar ratio of (A) to (B) is 1: 0.99;
(2) will be provided with
Figure BDA00027416563800000714
Adding the mixture into water and crushed ice, stirring, keeping the temperature at 0-5 ℃, adding hydrochloric acid, adding sodium nitrite, reacting for 1.5 hours to obtain a second mixed solution, wherein,
Figure BDA00027416563800000715
the feeding molar ratio of HCl to sodium nitrite is 1:1.0: 1.01;
(3) adding the second mixed solution obtained in the step (2) into the first mixed solution obtained in the step (1), adding sodium bicarbonate to adjust the pH value to 5.5-6.0, and reacting at 10-15 ℃ for 6h to obtain a third mixed solution, wherein the feeding of the first mixed solution and the second mixed solution is carried out according to the proportion
Figure BDA0002741656380000081
And
Figure BDA0002741656380000082
the feeding molar ratio of (1: 0.99);
(4) will be provided with
Figure BDA0002741656380000083
Adding the third mixed solution obtained in the step (3), adding sodium bicarbonate to adjust the pH value to 5.5-6.0, reacting for 3 hours at the temperature of 40-45 ℃ to obtain a fourth mixed solution, wherein,
Figure BDA0002741656380000084
and
Figure BDA0002741656380000085
the feeding molar ratio of (A) to (B) is 1: 2.0;
(5) will be provided with
Figure BDA0002741656380000086
Adding the mixture into the fourth mixed solution obtained in the step (4), adding sodium carbonate to adjust the pH value to 5.5-6.0, reacting at 75-80 ℃ for 6h to obtain a fifth mixed solution, wherein,
Figure BDA0002741656380000087
and
Figure BDA0002741656380000088
the feeding molar ratio of (1: 2.5);
(6) and (5) drying the fifth mixed solution obtained in the step (5) to obtain the product, namely the reactive dye red.
The structural formula of the product is as follows:
Figure BDA0002741656380000089
example 4
The reactive dye red provided in this example is prepared by the following method:
(1) will be provided with
Figure BDA00027416563800000810
Adding into crushed ice and water, stirring, and adding
Figure BDA00027416563800000811
Adding sodium bicarbonate to adjust the pH value to 2.0-2.5, reacting for 4 hours at the temperature of 5-10 ℃ to obtain a first mixed solution, wherein,
Figure BDA00027416563800000812
and
Figure BDA00027416563800000813
the feeding molar ratio of (A) to (B) is 1: 0.99;
(2) will be provided with
Figure BDA00027416563800000814
Adding the mixture into water and crushed ice, stirring, keeping the temperature at 0-5 ℃, adding hydrochloric acid, adding sodium nitrite, reacting for 1.5 hours to obtain a second mixed solution, wherein,
Figure BDA00027416563800000815
the feeding molar ratio of HCl to sodium nitrite is 1:1.0: 1.01;
(3) adding the second mixed solution obtained in the step (2) into the stepAdding sodium bicarbonate into the first mixed solution obtained in the step (1) to adjust the pH value to 5.5-6.0, and reacting at 10-15 ℃ for 5h to obtain a third mixed solution, wherein the feeding of the first mixed solution and the second mixed solution is carried out according to the proportion
Figure BDA0002741656380000091
And
Figure BDA0002741656380000092
the feeding molar ratio of (1: 0.99);
(4) will be provided with
Figure BDA0002741656380000093
Adding the third mixed solution obtained in the step (3), adding sodium bicarbonate to adjust the pH value to 5.5-6.0, reacting for 3 hours at the temperature of 30-35 ℃ to obtain a fourth mixed solution, wherein,
Figure BDA0002741656380000094
and
Figure BDA0002741656380000095
the feeding molar ratio of (A) to (B) is 1: 2.0;
(5) will be provided with
Figure BDA0002741656380000096
Adding the mixture into the fourth mixed solution obtained in the step (4), adding sodium carbonate to adjust the pH value to 5.5-6.0, reacting at 75-80 ℃ for 7h to obtain a fifth mixed solution, wherein,
Figure BDA0002741656380000097
and
Figure BDA0002741656380000098
the feeding molar ratio of (1: 2.5);
(6) and (5) drying the fifth mixed solution obtained in the step (5) to obtain the product, namely the reactive dye red.
The structural formula of the product is as follows:
Figure BDA0002741656380000099
comparative example 1
Commercially available reactive dye red has the following structural formula:
Figure BDA00027416563800000910
performance testing
1. Preparation of dyeing liquor
The reactive dyes of examples 1-4 and comparative example 1 were mixed according to the dyeing depth of 2% o.w.f, the anhydrous sodium sulphate dosage of 60g/l, the bath ratio of 1: 10, preparing each dyeing solution for later use.
2. Dyeing process (pure cotton)
The dyeing process using the dyeing solutions of examples 1 to 4 comprises: the dyeing liquid prepared by the reactive dyes of the embodiments 1 to 4 is heated, and pure cotton is dyed, washed and soaped, so that dyeing is completed.
Dyeing process using the dyeing liquor of comparative example 1: the dyeing liquid prepared by the reactive dye of the comparative example 1 is heated, and the sodium carbonate (the dosage is 20g/l) is added to dye, wash and soap the pure cotton, thus completing the dyeing.
3. Optimal coloring temperature determination
The dyeing solutions prepared by using the reactive dyes of example 1 and comparative example 1 were used to dye 12 cotton pieces of the same color at 60 ℃, 80 ℃, 100 ℃, 110 ℃, 120 ℃ and 130 ℃ respectively according to the above dyeing process, the color yields of the 12 dyed cotton pieces were measured respectively, and the relative color yields of the cotton pieces at 60 ℃, 80 ℃, 100 ℃, 110 ℃ and 120 ℃ were calculated respectively using the color yields at 130 ℃ as a reference standard, and the results are shown in table 1.
Table 1 shows the comparison of the optimum coloring temperatures of the reactive dye of example 1 with the reactive dye of comparative example 1
Figure BDA0002741656380000101
As can be seen from Table 1, the optimum coloring temperature of the reactive dye of example 1 is 100-130 ℃.
The dyeing liquid prepared by the active dyes of the embodiments 2 to 4 is used for dyeing different pure cotton with the same color at the temperature of 60 ℃, 80 ℃, 100 ℃, 110 ℃, 120 ℃ and 130 ℃, and the finally obtained optimal coloring temperature is also 100 to 130 ℃.
As can be seen from the above, the reactive dyes of examples 1 to 4 of the present invention have an optimum dyeing temperature of 100 to 130 ℃ which is the same as the dyeing temperature (110 to 130 ℃) of the disperse dye, and can be mixed with the disperse dye to perform one-bath dyeing. In addition, the reactive dyes of the embodiments 1 to 4 of the invention do not need to be added with soda ash for color fixation when being dyed.
The best coloring temperature of the existing common reactive dye is about 60 ℃, the dye cannot be simultaneously dyed with the disperse dye in one bath, and sodium carbonate is added for fixation during dyeing, so that the dyeing cost is increased, and the sewage and sludge treatment cost is also increased.
4. Testing of light resistance, wash resistance, perspiration resistance, friction resistance, hot press resistance, solubility
1) Respectively heating the dyeing solution prepared by the reactive dyes in the embodiments 1-4 to 100 ℃, carrying out heat preservation on pure cotton for 40min for dyeing, cooling, washing and soaping, and finishing dyeing.
2) The dyeing liquid prepared by the reactive dye of the comparative example 1 is heated to 60 ℃, pure cotton is dyed, sodium carbonate (20g/l) is added for fixation, the temperature is kept for 40min, and the dyeing is finished after cooling, washing and soaping.
The dyed pure cotton cloth was subjected to performance test, and the results are shown in table 2.
Table 2 shows the performance tests of the reactive dye reds of examples 1 to 4 and comparative example 1
Figure BDA0002741656380000111
As can be seen from Table 2, the reactive dyes of examples 1 to 4 of the present invention have the same or better fastness than the conventional reactive dyes at 60 ℃ when dyed at a high temperature of 100 ℃. As is clear from the above Table 1, the dyeing properties of the conventional reactive dyes are poor when the dyes are dyed at a high temperature of 100 ℃.
The above performance tests were performed using the following criteria:
1) color fastness to rubbing: GB/T3920-
2) Color fastness to perspiration: GB/T3922-
3) Color fastness to light: GB/T8427. 2008. method 3
4) Color fastness to washing: GB/T3921-
5) Heat resistance at 200 ℃: GB/T6152-1997.
6) Solubility: GB/T21879-2015.
5. Polyester cotton one-bath dyeing
At room temperature, the reactive dye of example 1 was dyed at a depth of 2% o.w.f, the commercially available disperse dye red T-2B (wujiang peach-derived dye) was dyed at a depth of 0.96o.w.f, anhydrous sodium sulphate 60g/l, bath ratio 1: 10 preparing a staining solution. Heating the dyeing solution to 110-.
The result shows that the cloth surface color is full when the example 1 and the disperse dye red T-2B are dyed in one bath, and the polyester and cotton dyeing has no color difference, so that the effect of dyeing by a two-bath method can be achieved.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

Claims (10)

1. A reactive dye red, characterized in that: the structure of the reactive dye red is shown as the general formula (I):
Figure FDA0002741656370000011
in the formula:
R1、R2、R3、R4each independently selected from H or an alkali metal cation;
M1、M2、M3、M4each independently selected from X, SO3X is alkyl with 1-5 carbon atoms or alkoxy with 1-5 carbon atoms, and X is H or alkali metal cation;
F1、F2each independently selected from Y, SO3Y、
Figure FDA0002741656370000013
Y is H or alkali metal cation, and m and n are respectively and independently selected from integers between 1 and 5;
A1、A2each independently selected from H or an alkali metal cation.
2. A reactive dye red according to claim 1, characterized in that: the alkali metal cation is Na, K or Li.
3. A reactive dye red according to claim 1, characterized in that: the M is1、M2、M3、M4Each independently selected from H, SO3H、SO3Na、SO3K、SO3Li、CH3O or CH3(ii) a Said F1、F2Each independently selected from H, SO3H、SO3Na、SO3K、SO3Li、SO2C2H5、SO2C2H4Na、SO2C2H4K、SO2C2H4Li、SO2C2H4OSO3H、SO2C2H4OSO3Na、SO2C2H4OSO3K or SO2C2H4OSO3Li。
4. A reactive dye red according to claim 1, characterized in that: the compound shown in the general formula I is one of the compounds shown in the following structural formula:
Figure FDA0002741656370000012
Figure FDA0002741656370000021
5. the preparation method of the reactive dye red is characterized by comprising the following steps:
(1) carrying out primary condensation reaction on a compound shown as a formula II and a compound shown as a formula III to obtain a condensate;
(2) carrying out diazo reaction on the compound shown in the formula IV under the action of nitrous acid to obtain a first intermediate;
(3) carrying out coupling reaction on the first condensate and the first intermediate to obtain a second intermediate;
(4) carrying out secondary condensation reaction on the second intermediate and a compound shown as a formula V to obtain a secondary condensate;
(5) carrying out tertiary condensation reaction on the secondary condensate and a compound shown as a formula VI to obtain reactive dye red;
Figure FDA0002741656370000031
M1、M2each independently selected from X1、SO3X1An alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, wherein X is1Is H or an alkali metal cation;
f is selected from Y1、SO3Y1、
Figure FDA0002741656370000032
Said Y is1Is H or alkali metal cation, m and n are respectively and independently selected from integers between 1 and 5;
R1、R2are independently selected from H or alkali metal cation;
a is selected from H or an alkali metal cation.
6. The method of claim 5, wherein M is selected from the group consisting of1、M2Each independently selected from H, SO3H、SO3Na、SO3K、SO3Li、CH3O or CH3(ii) a F is selected from H, SO3H、SO3Na、SO3K、SO3Li、SO2C2H5、SO2C2H4Na、SO2C2H4K、SO2C2H4Li、SO2C2H4OSO3H、SO2C2H4OSO3Na、SO2C2H4OSO3K or SO2C2H4OSO3Li。
7. A process for the preparation of reactive dye red according to claim 5, characterized in that: the alkali metal cation is Na, K or Li.
8. A process for the preparation of reactive dye red according to claim 5, characterized in that: the specific implementation process of the step (1) is as follows: mixing the compound shown in the formula II and the compound shown in the formula III with water, and stirring at the pH value of 1.5-3.0 and the temperature of 0-15 ℃ for reaction to prepare the first condensate, wherein the feeding molar ratio of the compound shown in the formula II to the compound shown in the formula III is 1: 0.97-1.02;
the specific implementation process of the step (2) is as follows: mixing the compound shown in the formula IV, hydrochloric acid, nitrite and water, and stirring for reaction at 0-15 ℃ to obtain the first intermediate, wherein the feeding molar ratio of the compound shown in the formula IV, HCl and nitrite ions is 1 (1-2.5) to 1-1.1;
in the step (3), feeding the first condensate and the first intermediate according to the feeding molar ratio of the compound shown in the formula III to the compound shown in the formula IV of 1: 0.97-1.01, and carrying out the coupling reaction at the pH value of 4.5-7.0 and the temperature of 10-20 ℃;
in the step (4), the feeding molar ratio of the compound shown in the formula V to the compound shown in the formula II is 1: 2.0-2.1, and the secondary condensation reaction is carried out at a pH value of 4.5-6.0 and a temperature of 30-45 ℃;
in the step (5), the feeding molar ratio of the compound shown in the formula II to the compound shown in the formula VI is 1: 2.0-3.5, and the tertiary condensation reaction is carried out at a pH value of 5.0-7.0 and a temperature of 75-90 ℃.
9. A process for preparing a reactive dye red according to any one of claims 5 to 8, wherein the process comprises the steps of:
(1) mixing the compound shown in the formula II and the compound shown in the formula III with ice water, adding weak base to adjust the pH value to 1.5-3.0, and then stirring and reacting for 2-4 h at 0-15 ℃ to obtain a first reaction liquid, wherein the weak base is one or more of sodium bicarbonate, potassium bicarbonate and lithium bicarbonate;
(2) mixing the compound shown in the formula IV, hydrochloric acid, sodium nitrite and ice water, and stirring and reacting for 1-3 hours at 0-15 ℃ to obtain a second reaction solution;
(3) mixing the first reaction solution and the second reaction solution, adding weak base to adjust the pH value to 4.5-7.0, and reacting for 4-6 h at 10-20 ℃ to obtain a third reaction solution, wherein the weak base is one or more of sodium bicarbonate, potassium bicarbonate and lithium bicarbonate;
(4) adding the compound shown in the formula V into the third reaction liquid, adding weak base to adjust the pH value to be 4.5-6.0, and reacting for 2-5 hours at the temperature of 30-45 ℃ to obtain a fourth reaction liquid, wherein the weak base is one or more of sodium bicarbonate, potassium bicarbonate and lithium bicarbonate;
(5) adding the compound shown in the formula VI into the fourth reaction liquid, adding a strong base to adjust the pH value to be 5.0-7.0, and reacting at 75-90 ℃ for 6-9 h to obtain a fifth reaction liquid, wherein the strong base is one or more of sodium carbonate, lithium carbonate and potassium carbonate;
(6) and drying the fifth reaction solution to obtain the reactive dye red.
10. Use of the reactive dye red of any one of claims 1 to 4 in pure cotton, rayon, T/R or T/C blended fabrics.
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