CN111925666A - High-solarization red reactive dye and preparation method thereof - Google Patents

High-solarization red reactive dye and preparation method thereof Download PDF

Info

Publication number
CN111925666A
CN111925666A CN202010842538.2A CN202010842538A CN111925666A CN 111925666 A CN111925666 A CN 111925666A CN 202010842538 A CN202010842538 A CN 202010842538A CN 111925666 A CN111925666 A CN 111925666A
Authority
CN
China
Prior art keywords
formula
reaction
reactive dye
controlled
red reactive
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202010842538.2A
Other languages
Chinese (zh)
Inventor
卢林德
蒋志平
孟胜锋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang Yide New Material Co Ltd
Original Assignee
Zhejiang Yide New Material Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhejiang Yide New Material Co Ltd filed Critical Zhejiang Yide New Material Co Ltd
Priority to CN202010842538.2A priority Critical patent/CN111925666A/en
Publication of CN111925666A publication Critical patent/CN111925666A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • 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
    • C09B62/515—Metal complex azo 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
    • C09B62/08—Azo dyes
    • C09B62/095—Metal complex azo 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
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
    • C09B67/0046—Mixtures of two or more azo dyes
    • C09B67/0051—Mixtures of two or more azo dyes mixture of two or more monoazo dyes
    • C09B67/0052—Mixtures of two or more reactive monoazo dyes
    • C09B67/0054—Mixtures of two or more reactive monoazo dyes all the reactive groups not being directly attached to a heterocyclic system
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/0072—Preparations with anionic dyes or reactive dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/0079—Azoic dyestuff preparations

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Coloring (AREA)

Abstract

The invention discloses a high-solarization red reactive dye and a preparation method thereof, belonging to the field of reactive dyes in new material technology. The high-solarization red reactive dye is a mixture compounded by one or more than two structures in a general formula of a formula (1) according to any proportion; one shown in the formula (1) is selected from any one or a mixture of more than two of the following structural formulas: wherein in formula (1): r1represents-SO3M；R2represents-H, -CH3or-CH2CH3；R3represents-H, -CH3、‑CH2CH3、‑SO3M、‑SO2CH＝CH2or-SO2C2H4OSO3M; m represents-H, -Na, -K or-Li; x represents Cl or F. The high-light-fastness red reactive dye has the advantages of high light fastness and high heat-resisting stability, and simultaneously has good rubbing fastness and washing fastness.

Description

High-solarization red reactive dye and preparation method thereof
Technical Field
The invention belongs to the field of reactive dyes in new material technology, and particularly relates to a high-solarization red reactive dye and a preparation method thereof.
Background
The occupancy rate of the reactive dye on the market is increasing at present, and people pay more attention to the research of the reactive dye. Reactive dye research began in 1956, and has been half a century to date. In recent years, a plurality of review articles about reactive dyes are published, the development of the reactive dyes is related, the application performance and the process of the reactive dyes are also included, the application performance and the environmental protection are mainly improved, the light fastness is particularly emphasized on the application performance, the light fastness is taken as an important assessment index in many product standards of China and the world textile industry, and under the background of new requirements and standards for the light fastness of textiles at home and abroad, high-quality high-light-fastness dyes must be developed to be applied to the textiles in a matched manner.
The general red reactive dyes all use H acid and J acid as coupling components to be combined with various aromatic amine diazo components to form a color development matrix, the light fastness of most of the red reactive dyes is relatively poor, and the general light fastness is only 2-3 grades, so that the requirements of customers on the light fastness performance are often difficult to meet.
Disclosure of Invention
The first invention aims to provide a red reactive dye with high light fastness, and meanwhile, the rubbing fastness and the washing fastness are better than those of the conventional red reactive dye.
Based on the first object, the second object of the present invention is to provide a preparation method of the high-solarization red reactive dye.
Based on the high-sunburn red reactive dye provided by the first invention object, the third invention object of the invention is also to provide another high-sunburn red reactive dye improved by an auxiliary agent.
In order to realize the three technically related invention purposes, the invention adopts the technical scheme that:
a high-light-fastness red reactive dye comprises any one compound selected from a general formula (1), or a mixture formed by compounding any more than two compounds in the general formula (1) according to any proportion;
Figure BDA0002641958330000021
wherein in formula (1):
R1represents-SO3M；
R2represents-H, -CH3、-CH2CH3；
R3represents-H, -CH3、-CH2CH3、-SO3M、-SO2CH＝CH2、-SO2C2H4OSO3M；
M represents-H, -Na, -K or-Li;
x represents Cl or F.
Preferably, the method comprises the following steps: r2is-H, -CH2CH3；R3is-SO3M、-SO2C2H4OSO3M; m is-Na; and X is Cl.
Specifically, the high-solarization red reactive dye shown in the formula (1) is one or a mixture of any more specific structural formulas in the following formulas (1-1) to (1-16):
Figure BDA0002641958330000022
Figure BDA0002641958330000031
Figure BDA0002641958330000041
Figure BDA0002641958330000051
a preparation method of the high-solarization red reactive dye adopts the following raw materials: hydrochloric acid, sodium nitrite, baking soda, copper sulfate, formula (I), formula (II), formula (III) and formula (IV).
Figure BDA0002641958330000061
Wherein in formula (I), formula (II), formula (III), formula (IV):
R1represents-SO3M；
R2represents-H, -CH3、-CH2CH3；
R3represents-H, -CH3、-CH2CH3、-SO3M、-SO2CH＝CH2、-SO2C2H4OSO3M；
M represents-H, -Na, -K or-Li;
x represents Cl or F.
The preparation method comprises the following steps:
a. diazotization reaction: diazotizing a formula (II) under the action of sodium nitrite and hydrochloric acid;
Figure BDA0002641958330000062
b. coupling reaction: carrying out coupling reaction on the diazotization reaction product of the formula (II) and the formula (I);
Figure BDA0002641958330000063
c. copper complex reaction: c, carrying out copper complex reaction on the coupling compound obtained in the step b under the action of copper sulfate;
Figure BDA0002641958330000064
d. a condensation reaction: c, carrying out a condensation reaction on the copper complex synthesized by the reaction in the step c and the formula (III);
Figure BDA0002641958330000071
e. carrying out secondary condensation reaction: carrying out a secondary condensation reaction on the primary condensation product synthesized by the reaction of the formula (IV) and the step d, and obtaining the high-solarization red reactive dye shown in the formula (A) after the reaction is finished;
Figure BDA0002641958330000072
formula (A):
Figure BDA0002641958330000073
that is, M in formula (A) represents M in formula (1): -the class of Na;
r in the formula (1) as defined in claim 13represents-SO2CH＝CH2The preparing step further comprises:
f. and (3) performing a de-esterification reaction, namely heating the synthesized dye of the formula (A) in the fe step to a certain temperature, and performing an alkali treatment reaction to obtain a dye of the formula (B):
Figure BDA0002641958330000081
preferably, the method comprises the following steps: the diazotization reaction in the step a needs to be carried out under the action of sodium nitrite and hydrochloric acid, the temperature is controlled to be 0-20 ℃, and the pH value is controlled to be 0.5-1.5. (ii) a
Step b, the coupling reaction is carried out under the action of sodium carbonate, the temperature is controlled to be 0-20 ℃, and the pH is controlled to be 6.5-8.5;
the copper complex reaction in the step c needs to be carried out simultaneously with the coupling reaction in the step b under the action of sodium carbonate, the temperature is controlled to be 0-20 ℃, and the pH value is controlled to be 6.5-8.5;
the first condensation reaction in the step d is carried out under the action of baking soda, the reaction temperature is controlled to be 0-20 ℃, and the pH value is controlled to be 5.5-7.5;
the second condensation reaction in the step e is carried out under the action of baking soda, the reaction temperature is controlled to be 35-55 ℃, and the pH value is controlled to be 5.5-7.5.
And step f, the step of degreasing reaction is to heat the synthesized dye to 50-70 ℃, adjust the pH value to 8.0-9.0 by using soda powder, perform alkali treatment reaction, and add hydrochloric acid to adjust the pH value to 5.0-6.5 after the end point of the degreasing reaction.
The other high-light-fastness red reactive dye is formed by mixing the high-light-fastness red reactive dye and an auxiliary agent; the auxiliary agent is one or a mixture of more than two of anhydrous sodium sulphate, sodium hexametaphosphate, a naphthalenesulfonic acid aniline condensation compound and a naphthalenesulfonic acid aniline condensation compound; further, the auxiliary agent is anhydrous sodium sulphate.
Compared with the prior art, the invention has the following beneficial effects:
firstly, the high-light red reactive dye is obtained by selecting or mixing the formula (1), and is suitable for dyeing cellulose fibers. Compared with the Chinese patent application with the application number of 201410384501.4 and the name of the reactive red dye composition, the reactive red dye, the preparation method and the application thereof, the invention carries out copper complex reaction on the structure of the dye, improves the sunlight color degradation resistance of the dye, and further improves the high light fastness of the dye. Meanwhile, the invention adopts an H acid structure which is very easy to oxidize, so that the light fastness and the heat-resistant stability of the dye have defects.
The high-light-fastness red reactive dye also has excellent coloring synchronism, high dye-uptake and color fixing rate and high level-dyeing property, and is particularly suitable for dyeing cotton fibers with high requirements on washing fastness, rubbing fastness, light fastness and heat-resisting stability. The obtained dyed fabric has the excellent performances of stable heat sensitivity, sun resistance, washing resistance, friction resistance and the like.
And thirdly, the invention adopts copper complex reaction, and improves the light fastness of the dye due to the improvement of the sunlight color degradation resistance of the dye, and the light fastness of the dye is better than that of the common dye without copper complex. Meanwhile, sulfonated J acid is used as a coupling component, and the structure has better light fastness and heat stability than the common dye using H acid as the coupling component.
And fourthly, in order to better improve the dyeing effects of water solubility, leveling property and the like of the dye, the dye can be added with different types of additives for additive improvement, and after the dye is added with different additives, the dye has better effects on the aspects of dyeing rate, dye diffusion rate, alkali resistance and the like after being used for dyeing fabrics.
Detailed Description
The following synthetic examples further illustrate the invention but do not therefore limit the scope of the invention, the dye compounds will be presented in the form of sodium salts for ease of illustration, but the actual form may be a metal base, more likely a metal salt, especially the free acid.
The technical solution of the present invention is illustrated by the following specific examples, but the scope of the present invention is not limited thereto:
example 1
A high-light-fastness red reactive dye is composed of a compound with a simple structure of a formula (1-1):
Figure BDA0002641958330000101
the synthesis method of the compound with the structure of (1-1) comprises the following steps:
1. diazotization reaction: 100g of ice water is added into a beaker, 25g of 2-aminophenol-4-sulfonic acid is added, the mixture is pulped for 1 hour, 12g of hydrochloric acid (30%) is added, 28g of sodium nitrite solution (30%) is slowly dripped, diazo reaction is carried out, the temperature is controlled to be 0-20 ℃, the pH value is controlled to be 0.5-1.5, and starch potassium iodide test paper is enabled to be micro-blue, while Congo high sun-dried red test paper is enabled to be micro-blue. After the dropwise addition of the sodium nitrite solution, the temperature is kept between 8 and 10 ℃, the pH value is controlled between 0.5 and 1.5, the reaction is stirred for 30 minutes, and then 0.5g of sulfamic acid is used for balancing the excessive sodium nitrite. The diazo reaction formula is shown as formula (a):
Figure BDA0002641958330000102
2. coupling reaction: adding 35g of sulfonated J acid into 200g of water, firstly adjusting the pH to 6.5-8.5 by 7g of soda ash, and slowly adding the sulfonated J acid into the diazonium salt obtained in the step 1, wherein the temperature is controlled to be 0-20 ℃ and the pH value is controlled to be 6.5-8.5 in the coupling process. The coupling reaction equation is shown in the following formula (b):
Figure BDA0002641958330000103
3. copper complex reaction: and (3) adding 30g of copper sulfate into the coupling compound obtained in the step (2) to perform copper complexing reaction, wherein the temperature is controlled to be 0-20 ℃ and the pH value is controlled to be 6.5-8.5 in the copper complexing process. The copper complex reaction equation is shown in (c) below:
Figure BDA0002641958330000111
4. a condensation reaction: adding 20g of cyanuric chloride into 200g of ice water, pulping for 1 hour, adding the copper complex obtained in the step 3, performing a condensation reaction, and controlling the pH value to be 5.5-7.5 and the temperature to be 0-20 ℃ by using 12g of sodium bicarbonate. The first reduction reaction equation is shown as the following formula (d):
Figure BDA0002641958330000112
5. carrying out secondary condensation reaction: 34g of para-ester was added to the condensate from step 4 above, and the pH was controlled to 5.5-7.5 with 15g of baking soda and the temperature was controlled to 35-55 ℃. The equation of the second condensation reaction is shown in (e) below:
Figure BDA0002641958330000113
example 2
A high-light-fastness red reactive dye is composed of a compound with a simple structure of a formula (1-6):
Figure BDA0002641958330000121
the synthesis method of the compound with the structure of (1-6) comprises the following steps:
1. diazotization reaction: 100g of ice water is added into a beaker, 25g of 2-aminophenol-5-sulfonic acid is added, the mixture is pulped for 1 hour, 12g of hydrochloric acid (30%) is added, 28g of sodium nitrite solution (30%) is slowly dripped, diazo reaction is carried out, the temperature is controlled to be 0-20 ℃, the pH value is controlled to be 0.5-1.5, and starch potassium iodide test paper is enabled to be micro-blue, while Congo high sun-dried red test paper is enabled to be micro-blue. After the dropwise addition of the sodium nitrite solution, the temperature is kept between 8 and 10 ℃, the pH value is controlled between 0.5 and 1.5, the reaction is stirred for 30 minutes, and then 0.5g of sulfamic acid is used for balancing the excessive sodium nitrite. The diazo reaction formula is shown as formula (a):
Figure BDA0002641958330000122
2. coupling reaction: adding 35g of sulfonated J acid into 200g of water, firstly adjusting the pH to 6.5-8.5 by 7g of soda ash, and slowly adding the sulfonated J acid into the diazonium salt obtained in the step 1, wherein the temperature is controlled to be 0-20 ℃ and the pH value is controlled to be 6.5-8.5 in the coupling process. The coupling reaction equation is shown in the following formula (b):
Figure BDA0002641958330000123
3. copper complex reaction: and (3) adding 30g of copper sulfate into the coupling compound obtained in the step (2) to perform copper complexing reaction, wherein the temperature is controlled to be 0-20 ℃ and the pH value is controlled to be 6.5-8.5 in the copper complexing process. The copper complex reaction equation is shown in (c) below:
Figure BDA0002641958330000131
4. a condensation reaction: adding 20g of cyanuric chloride into 200g of ice water, pulping for 1 hour, adding the copper complex obtained in the step 3, performing a condensation reaction, and controlling the pH value to be 5.5-7.5 and the temperature to be 0-20 ℃ by using 12g of sodium bicarbonate. The first reduction reaction equation is shown as the following formula (d):
Figure BDA0002641958330000132
5. carrying out secondary condensation reaction: 45g of N-ethyl meta-ester were added to the condensate from step 4 above, the pH was controlled to 5.5-7.5 with 15g of baking soda and the temperature was controlled to 35-55 ℃. The equation of the second condensation reaction is shown in (e) below:
Figure BDA0002641958330000133
example 3
A high-light-fastness red reactive dye is composed of a compound with a simple structure of a formula (1-12):
Figure BDA0002641958330000141
(1-12) the synthesis method of the compound with the structure comprises the following steps:
1. diazotization reaction: 100g of ice water is added into a beaker, 25g of 2-aminophenol-4-sulfonic acid is added, the mixture is pulped for 1 hour, 12g of hydrochloric acid (30%) is added, 28g of sodium nitrite solution (30%) is slowly dripped, diazo reaction is carried out, the temperature is controlled to be 0-20 ℃, the pH value is controlled to be 0.5-1.5, and starch potassium iodide test paper is enabled to be micro-blue, while Congo high sun-dried red test paper is enabled to be micro-blue. After the dropwise addition of the sodium nitrite solution, the temperature is kept between 8 and 10 ℃, the pH value is controlled between 0.5 and 1.5, the reaction is stirred for 30 minutes, and then 0.5g of sulfamic acid is used for balancing the excessive sodium nitrite. The diazo reaction formula is shown as formula (a):
Figure BDA0002641958330000142
2. coupling reaction: adding 35g of sulfonated J acid into 200g of water, firstly adjusting the pH to 6.5-8.5 by 7g of soda ash, and slowly adding the sulfonated J acid into the diazonium salt obtained in the step 1, wherein the temperature is controlled to be 0-20 ℃ and the pH value is controlled to be 6.5-8.5 in the coupling process. The coupling reaction equation is shown in the following formula (b):
Figure BDA0002641958330000143
3. copper complex reaction: and (3) adding 30g of copper sulfate into the coupling compound obtained in the step (2) to perform copper complexing reaction, wherein the temperature is controlled to be 0-20 ℃ and the pH value is controlled to be 6.5-8.5 in the copper complexing process. The copper complex reaction equation is shown in (c) below:
Figure BDA0002641958330000151
4. a condensation reaction: adding 20g of cyanuric chloride into 200g of ice water, pulping for 1 hour, adding the copper complex obtained in the step 3, performing a condensation reaction, and controlling the pH value to be 5.5-7.5 and the temperature to be 0-20 ℃ by using 12g of sodium bicarbonate. The first reduction reaction equation is shown as the following formula (d):
Figure BDA0002641958330000152
5. carrying out secondary condensation reaction: 26g of m-aminobenzenesulfonic acid was added to the condensate of the above step 4, and the pH was controlled to 5.5-7.5 with 15g of sodium bicarbonate and the temperature was controlled to 35-55 ℃. The equation of the second condensation reaction is shown in (e) below:
Figure BDA0002641958330000153
example 4
A high-light-fastness red reactive dye is composed of a compound with a simple structure of a formula (1-15):
Figure BDA0002641958330000161
(1-15) the synthesis method of the compound with the structure comprises the following steps:
1. diazotization reaction: 100g of ice water is added into a beaker, 25g of 2-aminophenol-4-sulfonic acid is added, the mixture is pulped for 1 hour, 12g of hydrochloric acid (30%) is added, 28g of sodium nitrite solution (30%) is slowly dripped, diazo reaction is carried out, the temperature is controlled to be 0-20 ℃, the pH value is controlled to be 0.5-1.5, and starch potassium iodide test paper is enabled to be micro-blue, while Congo high sun-dried red test paper is enabled to be micro-blue. After the dropwise addition of the sodium nitrite solution, the temperature is kept between 8 and 10 ℃, the pH value is controlled between 0.5 and 1.5, the reaction is stirred for 30 minutes, and then 0.5g of sulfamic acid is used for balancing the excessive sodium nitrite. The diazo reaction formula is shown as formula (a):
Figure BDA0002641958330000162
2. coupling reaction: adding 35g of sulfonated J acid into 200g of water, firstly adjusting the pH to 6.5-8.5 by 7g of soda ash, and slowly adding the sulfonated J acid into the diazonium salt obtained in the step 1, wherein the temperature is controlled to be 0-20 ℃ and the pH value is controlled to be 6.5-8.5 in the coupling process. The coupling reaction equation is shown in the following formula (b):
Figure BDA0002641958330000163
3. copper complex reaction: and (3) adding 30g of copper sulfate into the coupling compound obtained in the step (2) to perform copper complexing reaction, wherein the temperature is controlled to be 0-20 ℃ and the pH value is controlled to be 6.5-8.5 in the copper complexing process. The copper complex reaction equation is shown in (c) below:
Figure BDA0002641958330000171
4. a condensation reaction: adding 20g of cyanuric chloride into 200g of ice water, pulping for 1 hour, adding the copper complex obtained in the step 3, performing a condensation reaction, and controlling the pH value to be 5.5-7.5 and the temperature to be 0-20 ℃ by using 12g of sodium bicarbonate. The first reduction reaction equation is shown as the following formula (d):
Figure BDA0002641958330000172
5. carrying out secondary condensation reaction: 22g of o-toluidine were added to the condensate from step 4 above, and the pH was controlled to 5.5-7.5 with 15g of sodium bicarbonate and the temperature was controlled to 35-55 ℃. The equation of the second condensation reaction is shown in (e) below:
Figure BDA0002641958330000173
example 5
A high-light-fastness red reactive dye is composed of a compound with a simple structure of a formula (1-2):
Figure BDA0002641958330000181
the preparation method of the formula (1-2) adopts the following raw materials: hydrochloric acid, sodium nitrite, copper sulfate, baking soda, soda ash, o-aminophenol-4-sulfonic acid, sulfonated J acid, cyanuric chloride and meta-ester, and the preparation steps are the same as in examples 1, 2, 3 and 4.
Example 6
A high-light-fastness red reactive dye is composed of a compound with a simple structure of a formula (1-3):
Figure BDA0002641958330000182
the preparation method of the formula (1-3) adopts the following raw materials: hydrochloric acid, sodium nitrite, copper sulfate, baking soda, soda ash, 2-aminophenol-4-sulfonic acid, sulfonated J acid, cyanuric chloride and N-ethyl meta-ester, and the preparation steps are the same as in examples 1, 2, 3 and 4.
Example 7
A high-light-fastness red reactive dye is composed of a compound with a simple structure of a formula (1-4):
Figure BDA0002641958330000183
the preparation method of the formula (1-4) adopts the following raw materials: hydrochloric acid, sodium nitrite, copper sulfate, baking soda, soda ash, 2-aminophenol-4-sulfonic acid, sulfonated J acid, cyanuric fluoride, N-ethyl meta-ester, the preparation procedure was the same as in examples 1, 2, 3, 4.
Example 8
A high-light-fastness red reactive dye is composed of a compound with a simple structure of a formula (1-5):
Figure BDA0002641958330000191
the preparation method of the formula (1-5) adopts the following raw materials: hydrochloric acid, sodium nitrite, copper sulfate, baking soda, soda ash, 2-aminophenol-5-sulfonic acid, sulfonated J acid, cyanuric chloride and para-ester, and the preparation steps are the same as in examples 1, 2, 3 and 4.
Example 9
A high-light-fastness red reactive dye is composed of a compound with a simple structure of a formula (1-7):
Figure BDA0002641958330000192
the preparation method of the formula (1-7) adopts the following raw materials: hydrochloric acid, sodium nitrite, copper sulfate, baking soda, soda ash, 2-aminophenol-5-sulfonic acid, sulfonated J acid, cyanuric chloride and meta-ester, and the preparation steps are the same as in examples 1, 2, 3 and 4.
Example 10
A high-light-fastness red reactive dye is composed of a compound with a simple structure of a formula (1-8):
Figure BDA0002641958330000193
the preparation method of the formula (1-8) adopts the following raw materials: hydrochloric acid, sodium nitrite, copper sulfate, baking soda, soda ash, 2-aminophenol-5-sulfonic acid, sulfonated J acid, cyanuric fluoride and meta-ester, and the preparation steps are the same as in examples 1, 2, 3 and 4.
Example 11
A high-light-fastness red reactive dye is composed of a compound with a simple structure of a formula (1-9):
Figure BDA0002641958330000201
the preparation method of the formula (1-9) adopts the following raw materials: hydrochloric acid, sodium nitrite, copper sulfate, baking soda, soda ash, 2-aminophenol-5-sulfonic acid, sulfonated J acid, cyanuric chloride and metanilic acid, and the preparation steps are the same as in examples 1, 2, 3 and 4.
Example 12
A high-light-fastness red reactive dye is composed of a compound with a simple structure of a formula (1-10):
Figure BDA0002641958330000202
the preparation method of the formula (1-10) adopts the following raw materials: hydrochloric acid, sodium nitrite, copper sulfate, baking soda, soda ash, 2-aminophenol-5-sulfonic acid, sulfonated J acid, cyanuric chloride and sulfanilic acid, and the preparation steps are the same as in examples 1, 2, 3 and 4.
Example 13
A high-light-fastness red reactive dye is composed of a compound with a simple structure of a formula (1-11):
Figure BDA0002641958330000211
the preparation method of the formula (1-11) adopts the following raw materials: hydrochloric acid, sodium nitrite, copper sulfate, baking soda, soda ash, 2-aminophenol-4-sulfonic acid, sulfonated J acid, cyanuric chloride and sulfanilic acid, and the preparation steps are the same as in examples 1, 2, 3 and 4.
Example 14
A high-light-fastness red reactive dye is composed of a compound with a simple structure of a formula (1-13):
Figure BDA0002641958330000212
the preparation method of the formula (1-13) adopts the following raw materials: hydrochloric acid, sodium nitrite, copper sulfate, sodium bicarbonate, soda ash, 2-aminophenol-4-sulfonic acid, sulfonated J acid, cyanuric chloride and N-ethylaniline, the preparation steps of which were the same as in examples 1, 2, 3 and 4.
Example 15
A high-light-fastness red reactive dye is composed of a compound with a simple structure of a formula (1-14):
Figure BDA0002641958330000213
the preparation method of the formula (1-14) adopts the following raw materials: hydrochloric acid, sodium nitrite, copper sulfate, baking soda, soda ash, 2-aminophenol-4-sulfonic acid, sulfonated J acid, cyanuric chloride and o-ethylaniline, and the preparation steps thereof were the same as in examples 1, 2, 3 and 4.
Example 16
A high-light-fastness red reactive dye is composed of a compound with a simple structure of a formula (1-16):
Figure BDA0002641958330000221
the preparation method of the formula (1-16) adopts the following raw materials: hydrochloric acid, sodium nitrite, copper sulfate, baking soda, soda ash, 2-aminophenol-4-sulfonic acid, sulfonated J acid, melamine, metanilic acid, the preparation steps of which were the same as in examples 1, 2, 3, 4.
Example 17
A high-sunlight red reactive dye is prepared by mixing 80g of a compound with a structure shown in a formula (1-1) in example 1, 10g of a compound with a structure shown in a formula (1-2) in example 5 and 10g of a compound with a structure shown in a formula (1-3) in example 6 in a mixing barrel or dissolving the two together and then spray-drying.
Example 18
A high-light-fastness red reactive dye is prepared by mixing 50g of a compound with a structure shown in formula (1-12) in example 3, 5g of a compound with a structure shown in formula (1-9) in example 11, 5g of a compound with a structure shown in formula (1-11) in example 13 and 40g of a compound with a structure shown in formula (1-14) in example 15 with 10g of anhydrous sodium sulphate in a mixing barrel or dissolving the two together and then spray-drying the mixture.
Example 19
A high-light-fastness red reactive dye is prepared by mixing 50g of a compound with a structure shown in formula (1-4) in example 7, 20g of a compound with a structure shown in formula (1-5) in example 8, 10g of a compound with a structure shown in formula (1-7) in example 9 and 20g of a compound with a structure shown in formula (1-8) in example 10 with 20g of anhydrous sodium sulphate in a mixing barrel or dissolving the two together and then spray-drying the mixture.
Example 20
A high-light-fastness red reactive dye is prepared by mixing a mixture of 20g of a compound with a structure represented by the formula (1-12) in example 3 and 80g of a compound with a structure represented by the formula (1-15) in example 4 with 50g of anhydrous sodium sulphate in a mixing barrel, or dissolving the two together and then spray-drying.
Example 21
A high-light-fastness red reactive dye is prepared by mixing 50g of a compound with a structure represented by the formula (1-10) in example 12, 50g of a compound with a structure represented by the formula (1-16) in example 16 and 15g of sodium hexametaphosphate in a mixing barrel, or dissolving the two together and then spray-drying.
Partial dyeing examples of the above high-tanning red reactive dyes:
respectively weighing 1g of dye monomer compound prepared from the dyes (1-1) to (1-8) or a mixture of two or more of the dye monomer compound, placing the dye in a dyeing cup, dyeing the dye by 2 percent of the weight of the fabric, adsorbing the dye in a dyeing bath containing 60g/L of anhydrous sodium sulphate and having a bath ratio of 1:20 at 60 ℃ for 30min, and adding 15-20g/L of soda ash for color fixation for 45 min; or 1g of the dye monomer compound prepared from the dyes (1-9) to (1-16) is weighed respectively; or weighing 1g of the mixture prepared from the dyes (1-17) to (1-21) respectively, placing the dye accounting for 2% of the fabric weight in a dyeing cup, preparing the dye and printing paste into color paste, then printing, and steaming for 10min at 102 ℃. The dyed fabric is washed by water, soaped and dried. The obtained high-light-fastness red cotton cloth has uniform high light fastness, satisfactory light fastness and rubbing fastness, and the specific properties are shown in Table 1 (wherein the original change refers to the original cloth sample which is not washed at 95 ℃).
TABLE 1
Figure BDA0002641958330000231
Figure BDA0002641958330000241
According to a large number of light-fastness tests, the high-light-fastness red reactive dye is better than that of the traditional non-copper complex dye by 1-3 grades, and specific comparison data are shown in a table 2.
TABLE 2
Figure BDA0002641958330000242
Figure BDA0002641958330000251
Finally, it should also be noted that the above list is only a specific implementation example of the present invention. It is obvious that the invention is not limited to the above embodiment examples, but that many variations are possible. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.

Claims (7)

1. A high-solarization red reactive dye is characterized in that: the compound comprises any one compound selected from the general formula (1) or a mixture formed by compounding more than two compounds in the general formula (1) according to any proportion;
Figure FDA0002641958320000011
wherein in formula (1):
R1represents-SO3M；
R2represents-H, -CH3or-CH2CH3；
R3represents-H, -CH3、-CH2CH3、-SO3M、-SO2CH＝CH2or-SO2C2H4OSO3M；
M represents-H, -Na, -K or-Li;
x represents Cl or F.
2. The high-solarization red reactive dye according to claim 1, which is characterized in that: the high-solarization red reactive dye shown in the formula (1) is one or a mixture of any more specific structural formulas in the following formulas (1-1) to (1-16):
Figure FDA0002641958320000012
Figure FDA0002641958320000021
Figure FDA0002641958320000031
Figure FDA0002641958320000041
3. a process for preparing the high-insolation red reactive dye according to claim 1, wherein:
the following raw materials are adopted: hydrochloric acid, sodium nitrite, baking soda, sodium carbonate, copper sulfate, formula (I), formula (II), formula (III) and formula (IV).
Figure FDA0002641958320000051
Wherein in formula (I), formula (II), formula (III), formula (IV):
R1represents-SO3M；
R2represents-H, -CH3、-CH2CH3；
R3represents-H, -CH3、-CH2CH3、-SO3M、-SO2CH＝CH2、-SO2C2H4OSO3M；
M represents-H, -Na, -K or-Li;
x represents Cl or F.
The preparation method comprises the following steps:
a. diazotization reaction: diazotizing a formula (II) under the action of sodium nitrite and hydrochloric acid;
Figure FDA0002641958320000052
b. coupling reaction: carrying out coupling reaction on the diazotization reaction product of the formula (II) and the formula (I);
Figure FDA0002641958320000053
c. copper complex reaction: c, carrying out copper complex reaction on the coupling compound obtained in the step b under the action of copper sulfate;
Figure FDA0002641958320000054
d. a condensation reaction: c, carrying out a condensation reaction on the copper complex synthesized by the reaction in the step c and the formula (III);
Figure FDA0002641958320000061
e. carrying out secondary condensation reaction: carrying out a secondary condensation reaction on the primary condensation product synthesized by the reaction of the formula (IV) and the step d, and obtaining the high-solarization red reactive dye shown in the formula (A) after the reaction is finished;
Figure FDA0002641958320000062
formula (A):
Figure FDA0002641958320000063
that is, M in formula (A) represents M in formula (1): -the class of Na;
r in the formula (1) as defined in claim 13represents-SO2CH＝CH2The preparing step further comprises:
f. and (e) performing a de-esterification reaction, namely heating the dye of the formula (A) synthesized in the step (e) to a certain temperature, and performing an alkali treatment reaction to obtain a dye of the formula (B):
Figure FDA0002641958320000071
4. the preparation method of the high-solarization red reactive dye according to claim 3, characterized in that:
the diazotization reaction of the step a needs to be carried out under the action of sodium nitrite and hydrochloric acid, the temperature is controlled to be 0-20 ℃, and the pH value is controlled to be 0.5-1.5;
step b, the coupling reaction is carried out under the action of sodium carbonate, the temperature is controlled to be 0-20 ℃, and the pH is controlled to be 6.5-8.5;
the copper complex reaction in the step c needs to be carried out simultaneously with the coupling reaction in the step b under the action of sodium carbonate, the temperature is controlled to be 0-20 ℃, and the pH value is controlled to be 6.5-8.5;
the first condensation reaction in the step d is carried out under the action of baking soda, the reaction temperature is controlled to be 0-20 ℃, and the pH value is controlled to be 5.5-7.5;
the second condensation reaction in the step e is carried out under the action of baking soda, the reaction temperature is controlled to be 35-55 ℃, and the pH value is controlled to be 5.5-7.5.
5. The preparation method of the high-solarization red reactive dye according to claim 3, characterized in that:
and f, the step of the degreasing reaction is to heat the synthesized dye to 50-70 ℃, adjust the pH value to 8.0-9.0 by using soda powder, perform alkali treatment reaction, and add hydrochloric acid to adjust the pH value to 5.0-6.5 after the end point of the degreasing reaction is reached.
6. A high-solarization red reactive dye is characterized in that: the high-solarization red reactive dye is formed by mixing the high-solarization red reactive dye as claimed in claim 1 and an auxiliary agent; the auxiliary agent is selected from one or a mixture of more than two of anhydrous sodium sulphate, sodium hexametaphosphate, a methyl naphthalene sulfonic acid formaldehyde condensate and a naphthalene sulfonic acid formaldehyde condensate.
7. The high-solarization red reactive dye according to claim 6, which is characterized in that: the auxiliary agent is anhydrous sodium sulphate.
CN202010842538.2A 2020-08-20 2020-08-20 High-solarization red reactive dye and preparation method thereof Pending CN111925666A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010842538.2A CN111925666A (en) 2020-08-20 2020-08-20 High-solarization red reactive dye and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010842538.2A CN111925666A (en) 2020-08-20 2020-08-20 High-solarization red reactive dye and preparation method thereof

Publications (1)

Publication Number Publication Date
CN111925666A true CN111925666A (en) 2020-11-13

Family

ID=73305836

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010842538.2A Pending CN111925666A (en) 2020-08-20 2020-08-20 High-solarization red reactive dye and preparation method thereof

Country Status (1)

Country Link
CN (1) CN111925666A (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3065221A (en) * 1959-05-13 1962-11-20 Ici Ltd Copper complex monoazo dyes containing a monohalogenotriazinyl substituent
SU511546A1 (en) * 1974-01-09 1976-04-25 Ташкентский Институт Текстильной И Легкой Промышленности Method for determining sericin content in natural silk
CN102146061A (en) * 2010-02-09 2011-08-10 上海安诺其纺织化工股份有限公司 Red reactive dye compound, preparation method of red reactive dye compound and dye containing red reactive dye compound
CN102286219A (en) * 2011-06-17 2011-12-21 上海雅运纺织化工有限公司 Red active dye composition and dyeing application thereof in fibers

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3065221A (en) * 1959-05-13 1962-11-20 Ici Ltd Copper complex monoazo dyes containing a monohalogenotriazinyl substituent
SU511546A1 (en) * 1974-01-09 1976-04-25 Ташкентский Институт Текстильной И Легкой Промышленности Method for determining sericin content in natural silk
CN102146061A (en) * 2010-02-09 2011-08-10 上海安诺其纺织化工股份有限公司 Red reactive dye compound, preparation method of red reactive dye compound and dye containing red reactive dye compound
CN102286219A (en) * 2011-06-17 2011-12-21 上海雅运纺织化工有限公司 Red active dye composition and dyeing application thereof in fibers

Similar Documents

Publication Publication Date Title
CN115160823A (en) Reactive dye composition and dye product
EP2000511B1 (en) Trisazo reactive dyestuff compound
CN110157216B (en) Navy blue reactive dye and processing method thereof
JPH0562626B2 (en)
CN109370255B (en) Dark reactive dye composition and dye product
CN106634045A (en) Dark red reactive dye and preparation method thereof
CN111925666A (en) High-solarization red reactive dye and preparation method thereof
CN112409819B (en) Reactive dye red jade and application thereof
CN115304930A (en) Reactive dye composition and dye product
CN111320882B (en) Bright red reactive dye mixture and preparation method and application thereof
CN110054910B (en) Black reactive dye composition and preparation method and application thereof
CN109320996B (en) Composite active black dye mixture and application thereof
CN112480708A (en) Reactive dye red and preparation method and application thereof
CN113150576B (en) Ink-jet printing active red dye and preparation method and application thereof
CN110128846B (en) Navy blue reactive dye and preparation method thereof
JPH0334507B2 (en)
CN112574591B (en) Scarlet reactive dye and application thereof
JPS6036515B2 (en) Dyeing method for cellulose fibers
CN112300601B (en) Preparation method of active dye red jade
CN112175413B (en) Reactive dye blue and application thereof
JPH0118190B2 (en)
CN110229540B (en) Navy blue reactive dye and preparation process thereof
JPH0257826B2 (en)
CN114716844A (en) Composite high-solarization blue reactive dye and application thereof
CN117327406A (en) Composite high-light fastness reactive red dye composition and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20201113

RJ01 Rejection of invention patent application after publication