CN110878176B - Reactive dye compound and preparation method thereof - Google Patents

Reactive dye compound and preparation method thereof Download PDF

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CN110878176B
CN110878176B CN201910806855.6A CN201910806855A CN110878176B CN 110878176 B CN110878176 B CN 110878176B CN 201910806855 A CN201910806855 A CN 201910806855A CN 110878176 B CN110878176 B CN 110878176B
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compound
reaction
unsubstituted
halogen
independently selected
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CN110878176A (en
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姚成
马俊良
李寿椿
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Nanjing Tech University
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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
    • C09B62/78—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 with other reactive groups
    • C09B62/82—Azo dyes
    • C09B62/83—Disazo or polyazo dyes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C331/00—Derivatives of thiocyanic acid or of isothiocyanic acid
    • C07C331/16—Isothiocyanates
    • C07C331/32—Isothiocyanates having isothiocyanate groups acylated
    • 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
    • D06P3/666—Natural or regenerated cellulose 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
    • D06P3/68—Preparing azo dyes on the material

Abstract

The invention discloses a reactive dye compound and a preparation method thereof. The active group of the reactive dye is benzoyl isocyanate, can be used independently or in combination with other dyes, and has better dye uptake and color fastness on cotton fiber and silk. The dye can reduce the production cost and the energy consumption pressure, and is an environment-friendly dye suitable for clean production.

Description

Reactive dye compound and preparation method thereof
Technical Field
The invention particularly relates to a novel active radical dye compound and a preparation method thereof.
Background
The reactive dye is the most widely used dye in all dye classes due to the characteristics of bright color, excellent application performance, strong applicability and the like.
The reactive dye molecule contains one or more reactive groups capable of reacting with the fiber, and the reactive groups mainly comprise three main groups (s-triazine reactive group, vinyl sulfone reactive group and pyrimidine reactive group). Although the dye uptake and fastness of the dye are improved by the active groups in the dye molecules, the production cost of the active dye is indirectly improved due to the large molecular weight of the active groups. Therefore, the development of a reactive group with a smaller molecular weight can greatly reduce the production cost of the reactive dye.
The reactive dyes are various in types, the common reactive dyes need to be fixed at a higher temperature (for example, the following two dyes need to be fixed at 60 ℃), the energy consumption is higher, and the reactive dyes fixed at a lower temperature are easy to hydrolyze due to higher reactivity, so that the development of the reactive dyes which can be fixed at a low temperature and are not easy to hydrolyze is a problem which needs to be solved urgently by the market.
Figure BDA0002183915590000011
The active group in the dye is benzoyl isocyanate which has excellent binding performance with cellulose, and the compound I is taken as an example for illustration, and the specific principle is as follows:
Figure BDA0002183915590000012
disclosure of Invention
The invention discloses a novel reactive group reactive dye capable of fixing color at low temperature, which is characterized by high yield and good dye uptake and color fastness. The dye not only has lower production cost than other reactive dyes, but also can solve the problem of overlarge energy consumption in the printing and dyeing process. In addition, the invention also provides a preparation method and application of the dye.
In order to achieve the purpose, the invention adopts the following technical scheme:
the reactive dye has a reactive group of benzoyl isocyanate and a compound with a structure shown in a general formula (A);
Figure BDA0002183915590000021
wherein X represents
Figure BDA0002183915590000022
Wherein R is1、R2、R3And R4Each independently selected from H, halogen, heteroatom substituted or unsubstituted C1-20A hydrocarbyl group;
the preparation method of the reactive dye compound A comprises the following steps:
in the invention, firstly, a compound G is used as a raw material to synthesize an intermediate compound F, and the compound G and dichloro are used as solvents
The sulfoxide reaction is carried out to obtain:
Figure BDA0002183915590000023
wherein R is1、R2、R3And R4Each independently selected from H, halogen, heteroatom substituted or unsubstituted C1-20A hydrocarbyl group;
the following methods and conditions are particularly preferred in the above synthesis: and (3) reacting the compound G with thionyl chloride in a dichloromethane solution under the condition of using dimethylformamide as a catalyst. The molar ratio of the compound G to the thionyl chloride is preferably 1: 3; the reaction temperature is preferably 0-5 ℃; the reaction time is preferably 3 to 3.5 hours. After the reaction is finished, the reaction solution is evaporated to dryness at 30 ℃ to obtain the product.
The invention takes a compound F as a raw material to synthesize an intermediate compound E, and the intermediate compound E is obtained by reacting the compound F with ammonium thiocyanate by taking acetone as a solvent:
Figure BDA0002183915590000031
wherein R is1、R2、R3And R4Each independently selected from H, halogen, heteroatom substituted or unsubstituted C1-20A hydrocarbyl group;
the above reaction process is preferably carried out by the following method and conditions: and (3) reacting the compound F with ammonium thiocyanate in an anhydrous acetone solution under a reflux condition to obtain the compound. The molar ratio of the compound F to the ammonium thiocyanate is preferably 1: 1.2; the reaction temperature is preferably 65-70 ℃; the reaction time is preferably 3 to 3.5 hours. After the reaction is finished, the reactant is subjected to rotary evaporation at the temperature of 30 ℃, and then washed for 2-3 times by water to obtain the product.
In the invention, the intermediate C synthesized by using the compound E as a raw material can be prepared by the following method: and (3) carrying out diazotization reaction on the compound E.
Figure BDA0002183915590000032
Wherein R is1、R2、R3And R4Each independently selected from H, halogen, heteroatom substituted or unsubstituted C1-20A hydrocarbyl group;
in the invention, the compound C and the compound D are subjected to coupling reaction to prepare the compound C;
Figure BDA0002183915590000033
x represents
Figure BDA0002183915590000034
Wherein R is1、R2、R3And R4Each independently selected from H, halogen, heteroatom substituted or unsubstituted C1-20A hydrocarbyl group;
the compound D is a commercial product.
The acidic coupling methods and conditions described are all conventional in the art for such reactions, and the following are particularly preferred in the present invention: in a solvent, controlling the pH value to be 3-3.5, and carrying out electrophilic substitution reaction on the compound D and the compound C; wherein, the solvent is preferably water; the reaction temperature is preferably 0-5 ℃; the reaction time is preferably measured until the reaction is complete, and is typically 2.5 hours.
In the present invention, the reactive dye compound A can be prepared by the following method: carrying out electrophilic substitution reaction on the compounds B and C;
Figure BDA0002183915590000041
x represents
Figure BDA0002183915590000042
Wherein R is1、R2、R3And R4Each independently selected from H, halogen, heteroatom substituted or unsubstituted C1-20A hydrocarbyl group;
wherein the methods and conditions for the basic coupling are all conventional in the art for such reactions, the following are particularly preferred in the present invention: in a solvent, controlling the pH value to be 8-8.5, and carrying out electrophilic substitution reaction on the compound B and the compound C; wherein, the solvent is preferably water; the reaction temperature is preferably 0-5 ℃; the reaction time is preferably determined until the reaction is complete, typically 2 hours.
Detailed Description
The preparation and synthesis of the compound shown as the following formula I:
Figure BDA0002183915590000043
(1) acylation of p-aminobenzoic acid
Dissolving 0.2mol of p-aminobenzoic acid (2.8g) in 20ml of dichloromethane, cooling to 0-5 ℃, slowly dripping 5ml of thionyl chloride into the cooled solution of the p-aminobenzoic acid, dripping 2 drops of anhydrous dimethylformamide solution serving as a reaction catalyst after the temperature of the solution is stabilized, reacting for 3 hours at the temperature of 0-5 ℃, and obtaining a yellow-green solution after the reaction is finished. The solution after the reaction is dried at 30 ℃ for the next reaction.
(2) Formation of benzoyl isocyanate reactive groups
The first step reaction product was dissolved in anhydrous acetone, 1.8g of ammonium thiocyanate was added thereto to completely dissolve it, and then reacted at 65 ℃ under reflux for 3 hours. The reacted solution is coffee suspension, the reacted solution is dried in a spinning mode at the temperature of 30 ℃, water is added for suction filtration, after the suction filtration is finished, the solution is washed twice by water and dried at the temperature of 60 ℃, and diazotization is prepared.
(3) Diazotization of p-aminobenzoyl isocyanate
0.02mol (3.7g) of the product obtained after the reaction in the second step is taken, and 50ml of ice water is added for pulping for 1 hour to ensure uniform dispersion. Adding 3ml of concentrated hydrochloric acid into the mixture under stirring, taking 1.5g of NaNO2 particles after the pH value of the mixture is stable to prepare a solution, slowly dripping the solution into the acidic solution of the p-aminobenzoyl isocyanate, and reacting at the temperature of 0-5 ℃ for 2 hours, wherein the solution after reaction is coffee suspension. And (3) dropwise adding 15% by mass of sulfamic acid solution into the solution after reaction, dropwise adding the sulfamic acid solution into the solution until no bubbles are generated in the solution, continuing to react for 10min, and then checking by using starch potassium iodide test paper until the potassium iodide test paper is not microscopically blue. After the reaction is finished, the diazotized solution is divided into two equal parts for coupling.
(4) Acid coupling
0.01mol (3.2g) of H acid is taken and added with 50ml of deionized water for pulping for 1 hour, and the solution becomes light yellow strip. The pH of the solution was adjusted to 7 by the addition of baking soda, at which time the solution became clear and dark brown. The dissolved solution is added into one part of the diazotized solution dropwise, the pH of the solution is adjusted to 3.5 by baking soda and the solution is reacted for 3 hours under ice bath conditions.
(5) Basic coupling
And quickly adding another part of the diazotized solution into the acid coupled solution, adjusting the pH value to 8 by using baking soda, and reacting for 3 hours under ice bath conditions. Adding 2g of salt into 100ml of the feed liquid, salting out, filtering, washing with ethanol for 2 times, and drying at 60 ℃ to obtain the product.
Refining and purifying the compound, and performing infrared spectroscopic analysis, wherein the wave number data of each functional group is 3333cm-1 (N-H); 1700cm-1(C＝O)；1507cm-1(N＝N)；1407cm-1(C-N heterocycle); 1241(C ═ S),1179cm-1(C-N aliphatic);
the dye compound A in the example related to the invention is dyed according to the conventional process, and the bath ratio is 1: 50. Firstly, stirring and dyeing cotton fabrics and dye liquor for 3min at room temperature, then heating to 40 ℃ at the speed of 2 ℃/min, and preserving heat for 100 min. Then the cotton fabric is taken out, washed by water and soaped (2g/L soap chips, 5 min). Wherein compound a is used in an amount of 10% (o.w.f); the dosage of the color fixing agent is 5g/L of soda ash; salt 15 g/L. The above dyeing process was carried out using pure cotton knitted fabric.
The dye uptake of the dye was measured by the above process and the color samples obtained were tested for fastness to washing and soaping using a Y571B model crockmeter and a dotacan 600 computer colorimeter, the results determined according to the standard of GB/T2391-2008 were as follows:
Figure BDA0002183915590000051

Claims (10)

1. a reactive dye compound having the structure
Figure FDA0002897776230000011
X represents
Figure FDA0002897776230000012
Wherein R is1、R2、R3And R4Each independently selected from H, halogen, heteroatom substituted or unsubstituted C1-20A hydrocarbyl group.
2. A process for preparing a reactive dye compound according to claim 1, comprising the steps of:
performing coupling reaction on the compound C and the compound B;
Figure FDA0002897776230000013
x represents
Figure FDA0002897776230000014
Wherein R is1、R2、R3And R4Each independently selected from H, halogen, heteroatom substituted or unsubstituted C1-20A hydrocarbyl group.
3. The method of claim 2, wherein: the reaction method and conditions are as follows: controlling the pH value in a reaction solvent to be 8-8.5, and carrying out electrophilic substitution reaction on the compound B and the compound C; wherein the solvent is water; the reaction temperature is 0-5 ℃; the reaction time was 2 hours until completion of the detection reaction.
4. The method of claim 2, wherein: the compound B can be prepared by the following method: carrying out coupling reaction on the compound C and H acid;
Figure FDA0002897776230000015
x represents
Figure FDA0002897776230000021
Wherein R is1、R2、R3And R4Each independently selected from H, halogen, heteroatom substituted or unsubstituted C1-20A hydrocarbyl group.
5. The method of claim 4, wherein: the reaction method and conditions are as follows: in a water solvent, controlling the pH value to be 3-3.5, and carrying out electrophilic substitution reaction on the compound D and the compound C; wherein the solvent is water; the reaction temperature is 0-5 ℃; the reaction time was 2.5 hours until completion of the detection reaction.
6. The method of claim 4, wherein: the compound C can be prepared by the following method: diazotizing the compound E to obtain the compound,
Figure FDA0002897776230000022
wherein R is1、R2、R3And R4Each independently selected from H, halogen, heteroatom substituted or unsubstituted C1-20A hydrocarbyl group.
7. The method of claim 6, wherein: the reaction method and conditions are as follows: in dilute acid water solution, carrying out diazotization reaction on the compound E, acid and sodium nitrite; wherein the dilute acid aqueous solution is dilute HCl; the mass fraction of the dilute acid aqueous solution is 30-40%; the molar ratio of the compound E to the sodium nitrite is 1: 1.06; the molar ratio of the compound E to the acid is 1: 3; the reaction temperature is 0-5 ℃; the reaction time is determined to be complete.
8. The method of claim 6, wherein: the compound E can be prepared by reacting a compound F with ammonium thiocyanate by using acetone as a solvent:
Figure FDA0002897776230000031
wherein R is1、R2、R3And R4Each independently selected from H, halogen, heteroatom substituted or unsubstituted C1-20A hydrocarbyl group.
9. The method of claim 8, wherein: the reaction method and conditions are as follows: reacting the compound F with ammonium thiocyanate in an anhydrous acetone solution under a reflux condition to obtain the compound F; the molar ratio of the compound F to the ammonium thiocyanate is 1: 1.2; the reaction temperature is 65-70 ℃; the reaction time is 3-3.5 hours; after the reaction is finished, the reactant is subjected to rotary evaporation at the temperature of 30 ℃, and then washed for 2-3 times by water to obtain the product.
10. The method of claim 9, wherein: the compound F is prepared by the following method that dichloromethane is used as a solvent to react the compound G with thionyl chloride to obtain:
Figure FDA0002897776230000032
wherein R is1、R2、R3And R4Each independently selected from H, halogen, heteroatom substituted or unsubstituted C1-20A hydrocarbyl group.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008074953A (en) * 2006-09-21 2008-04-03 Toppan Printing Co Ltd Method for producing reactive azo compound, reactive azo compound and reaction product thereof
WO2008092041A2 (en) * 2007-01-24 2008-07-31 Carnegie Mellon University Optical biosensors
CN101768373A (en) * 2010-01-08 2010-07-07 武汉科技学院 Method for preparing water soluble vinyl-sulfone polyurethane class high molecular reactive dye with diazo coupling method
CN109467673A (en) * 2018-09-10 2019-03-15 清华大学 A kind of enclosed type active anion colorful polyurethane emulsion and its preparation method and application

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008074953A (en) * 2006-09-21 2008-04-03 Toppan Printing Co Ltd Method for producing reactive azo compound, reactive azo compound and reaction product thereof
WO2008092041A2 (en) * 2007-01-24 2008-07-31 Carnegie Mellon University Optical biosensors
CN101768373A (en) * 2010-01-08 2010-07-07 武汉科技学院 Method for preparing water soluble vinyl-sulfone polyurethane class high molecular reactive dye with diazo coupling method
CN109467673A (en) * 2018-09-10 2019-03-15 清华大学 A kind of enclosed type active anion colorful polyurethane emulsion and its preparation method and application

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