CN110628237A - Preparation method of red reactive dye compound - Google Patents
Preparation method of red reactive dye compound Download PDFInfo
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- CN110628237A CN110628237A CN201910807391.0A CN201910807391A CN110628237A CN 110628237 A CN110628237 A CN 110628237A CN 201910807391 A CN201910807391 A CN 201910807391A CN 110628237 A CN110628237 A CN 110628237A
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- 239000000985 reactive dye Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 150000001875 compounds Chemical class 0.000 title claims description 7
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical group ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 12
- 238000009833 condensation Methods 0.000 claims description 10
- 230000005494 condensation Effects 0.000 claims description 10
- KYARBIJYVGJZLB-UHFFFAOYSA-N 7-amino-4-hydroxy-2-naphthalenesulfonic acid Chemical compound OC1=CC(S(O)(=O)=O)=CC2=CC(N)=CC=C21 KYARBIJYVGJZLB-UHFFFAOYSA-N 0.000 claims description 9
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 8
- 238000005859 coupling reaction Methods 0.000 claims description 7
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- 150000004982 aromatic amines Chemical class 0.000 claims description 6
- 230000008878 coupling Effects 0.000 claims description 6
- 238000010168 coupling process Methods 0.000 claims description 6
- 239000012954 diazonium Substances 0.000 claims description 6
- 150000001989 diazonium salts Chemical class 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000006193 diazotization reaction Methods 0.000 claims description 4
- 229940126062 Compound A Drugs 0.000 claims description 3
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 3
- 238000004537 pulping Methods 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000010288 sodium nitrite Nutrition 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 2
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000005185 salting out Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims 1
- 230000002378 acidificating effect Effects 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 239000008187 granular material Substances 0.000 claims 1
- 239000000975 dye Substances 0.000 abstract description 19
- 229920000742 Cotton Polymers 0.000 abstract description 4
- 230000007062 hydrolysis Effects 0.000 abstract description 3
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 3
- 239000000835 fiber Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000004043 dyeing Methods 0.000 description 5
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000007336 electrophilic substitution reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- OMRXVBREYFZQHU-UHFFFAOYSA-N 2,4-dichloro-1,3,5-triazine Chemical compound ClC1=NC=NC(Cl)=N1 OMRXVBREYFZQHU-UHFFFAOYSA-N 0.000 description 1
- HTSVYUUXJSMGQC-UHFFFAOYSA-N 2-chloro-1,3,5-triazine Chemical compound ClC1=NC=NC=N1 HTSVYUUXJSMGQC-UHFFFAOYSA-N 0.000 description 1
- 229910006069 SO3H Inorganic materials 0.000 description 1
- 159000000032 aromatic acids Chemical class 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- -1 compound arylamine Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000982 direct dye Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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
- C09B62/78—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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
Abstract
The invention discloses a red reactive dye which can be well colored with fibers in low-temperature and high-temperature environments, and has the advantages of simple preparation method and high yield; the reactive group of the reactive dye is cyanuric chloride, has the characteristics of the reactive dye under the low-temperature condition, and shows better substantivity due to the hydrolysis of the reactive group at high temperature. The dye can be used independently or in combination with other dyes, and has better dye uptake and dye fastness to cotton fibers.
Description
Technical Field
The invention particularly relates to a preparation method of a red reactive dye compound.
Background
The reactive dye is a dye with one or more reactive groups capable of chemically reacting with cellulose in a molecule, and has the characteristics of complete color spectrum, excellent color fastness, low price and the like. At present, triazine reactive dyes in the market of China mainly comprise an X type (the active group is dichloros-triazine) and a K type (the active group is monochloro-s-triazine), the K type reactive dye is not easy to hydrolyze but has higher color fixing temperature, the X type reactive dye is easy to hydrolyze at high temperature so that the color can be fixed only at low temperature, and the development of the triazine reactive dye is limited by the defects.
The invention synthesizes X-type active dye molecules with larger planes, and the dye molecules have the characteristics of active dyes and direct dyes due to the characteristic that cyanuric chloride active groups are hydrolyzed to generate hydroxyl groups. Thereby overcoming the problem of low dye uptake caused by hydrolysis of the X-type dye and simultaneously improving the fixation condition of the X-type reactive dye.
Disclosure of Invention
The invention mainly provides a new red reactive dye capable of fixing color within the temperature range of 30-90 ℃, which can solve the problem of hydrolysis of domestic X-type dye under the high-temperature condition and has excellent dyeing uptake and dyeing fastness. In addition, the invention also provides a preparation method and application of the dye.
In order to solve the technical problems, the invention adopts the following technical scheme:
the invention provides a red reactive dye, wherein the coupling component of the reactive dye is J acid, the diazo components are Laurencic acid and DSD acid respectively, and the active group is cyanuric chloride;
wherein,
a process for the preparation of the above compound comprising the steps of:
(1) by one-shot condensation
The primary condensation liquid can be prepared by the following method: the J acid and cyanuric chloride are subjected to substitution reaction at low temperature.
The following methods and conditions are particularly preferred: in the aqueous solution, J acid and cyanuric chloride react at low temperature. The molar ratio of J acid to cyanuric chloride is preferably 1: 1.2; the reaction temperature is preferably 0-5 ℃; the reaction time is preferably 3 to 3.5 hours.
(2) Diazotization
In the present invention, the diazonium salt can be prepared by the following method: diazotizing arylamine to obtain the compound arylamine diazotizer;
wherein,
wherein the methods and conditions of the diazotization reaction are all conventional in the art, the following methods and conditions are particularly preferred in the present invention: in dilute acid water solution, arylamine, acid and sodium nitrite are diazotized to obtain the product.
Wherein, the dilute acid aqueous solution is preferably dilute HCl; the mass fraction of the dilute acid aqueous solution is preferably 30-40%; the molar ratio of the arylamine to the sodium nitrite is preferably 1: 1.08; the molar ratio of aromatic amine and acid is preferably 1: 3; the reaction temperature is preferably 0-5 ℃; the reaction time is preferably set to detect completion of the reaction, and is generally 0.5 to 1 hour.
(3) And (3) alkaline coupling.
The dye molecule can be prepared by the following method: carrying out electrophilic substitution reaction on the diazonium salt prepared by the reaction and the primary condensation solution in an alkaline environment;
wherein,
wherein the methods and conditions of the electrophilic substitution reaction are conventional in the art, the following are particularly preferred in the present invention: controlling the pH value to be 6.5-7.0 in a solvent, and carrying out nucleophilic substitution reaction on the diazonium salt and the primary condensation solution; wherein, the solvent is preferably water; the molar ratio of the primary condensate to the diazonium salt is preferably 1: 1.2; the reaction temperature is preferably 0-5 ℃; the reaction time is preferably determined until the reaction is complete, typically 2 hours.
Detailed Description
Example 1
The preparation and synthesis of the compound shown as the following formula A':
adding 50ml of ice water into 0.02mol (3.680g) of cyanuric chloride, pulping for 1h to uniformly disperse the ice water, adding 0.02mol (4.785g) of J acid under stirring, adjusting the pH of the solution to 3-4, adding 1ml of sodium bicarbonate aqueous solution with the mass fraction of 30% every 20min in the reaction process, reacting for 4h at low temperature, and obtaining a primary condensation solution of cyanuric chloride and J acid, wherein the solution after the reaction is transparent and pale white.
0.01mol (3.704g) of DSD acid is taken, 50ml of ice water is added for beating for 1 hour to ensure uniform dispersion. 1ml of concentrated hydrochloric acid is added under the condition of stirring until the pH value is stable; taking NaNO21.4g of the particles are prepared into an aqueous solution, the aqueous solution is slowly dripped into the acid solution of the DSD acid, the reaction is carried out for 2 hours at the temperature of 0-5 ℃, and the reacted solution is yellow suspension. And (3) dropwise adding 15% sulfamic acid solution into the solution after the reaction, dropwise adding the sulfamic acid solution into the solution without bubbles, continuing the reaction for 10min, and checking by using starch potassium iodide test paper until the potassium iodide test paper is not microscopically blue.
Adding the diazotized solution into primary condensation liquid of cyanuric chloride and J acid under the condition of stirring, adjusting the pH of the reaction liquid to 7 by NaHCO3, and reacting for 2h under the condition of ice bath. Adding 2g NaCl into every 100ml of dye solution for salting out, performing suction filtration, washing with ethanol for 2-3 times, and drying.
Refining and purifying the compound A', and performing infrared spectroscopic analysis to obtain 3445cm wave number data of each functional group-1(N-H)；1551cm-1(N ═ N); 1498 (triazine); 1203. 1055cm-1(-SO3H)；λmax＝544nm
The dye compound A' in example 1 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 70 ℃ at the speed of 2 ℃/min, and carrying out heat preservation and dyeing for 100 min. Then the cotton fabric is taken out, washed by water and soaped (2g/L soap chips, 5 min). Wherein the amount of the dye compound is 10% (o.w.f); the dosage of the color fixing agent is as follows: 5g/L of soda ash and 15g/L of salt. 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:
Claims (2)
1. a preparation method of a red reactive dye comprises the following steps:
wherein,
the preparation method of the compound comprises the following steps:
(1) by one-shot condensation
Enabling cyanuric chloride to react with J acid at low temperature to prepare primary condensation liquid;
(2) diazotization
Diazotizing arylamine and sodium nitrite under acidic condition to obtain diazonium salt;
(3) basic coupling
And (3) coupling the prepared diazonium salt with the primary condensation solution in an alkaline environment to obtain a solution containing the compound A or A'.
2. The method according to claim 1, characterized by comprising the steps of:
(1) by one-shot condensation
50ml of ice water is taken and added with cyanuric chloride for pulping for 1 hour to disperse the ice water evenly. Adding J acid under the stirring condition, adjusting the pH value of the solution to 3-4, adding a sodium bicarbonate solution with the mass fraction of 30% every 20min in the reaction process, adjusting the pH value to about 3, and reacting for 4h at low temperature for coupling reaction;
(2) diazotization
Adding 50ml of ice water into arylamine (Laurenic acid or DSD acid) and pulping for 1 hour to uniformly disperse. Adding quantitative concentrated hydrochloric acid under stirring to stabilize pH, and collecting NaNO2Preparing the granules into a solution, slowly dripping the solution into the acid solution of the diazo component, and reacting for 2 hours at the temperature of 0-5 ℃. Dropwise adding 15% sulfamic acid solution into the reacted solution, dropwise adding the solution into the solution without bubbles, continuously reacting for 10min, and checking by using starch potassium iodide test paper until the potassium iodide test paper is not microscopically blue;
(3) basic coupling
And (3) quickly adding the diazotized solution into the solution after acid coupling, adjusting the pH of the solution to 7 by using sodium bicarbonate, and reacting for 3 hours under the ice bath condition. Adding 2g of salt into each 100ml of reaction solution, salting out, filtering, washing with ethanol for 2 times, and drying at 60 ℃ to obtain the product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910807391.0A CN110628237A (en) | 2019-08-29 | 2019-08-29 | Preparation method of red reactive dye compound |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910807391.0A CN110628237A (en) | 2019-08-29 | 2019-08-29 | Preparation method of red reactive dye compound |
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| Publication Number | Publication Date |
|---|---|
| CN110628237A true CN110628237A (en) | 2019-12-31 |
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|---|---|---|---|
| CN201910807391.0A Pending CN110628237A (en) | 2019-08-29 | 2019-08-29 | Preparation method of red reactive dye compound |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2904124A1 (en) * | 1979-02-03 | 1980-08-14 | Hoechst Ag | WATER-SOLUBLE, FIBER-REACTIVE DISAZO DYES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE FOR COLORING AND PRINTING FIBER MATERIALS CONTAINING HYDROXY GROUPS AND CARBONAMID GROUPS |
| US5831039A (en) * | 1997-04-15 | 1998-11-03 | Dystar Textilfarben Gmbh & Co. Deutschland Kg | Fiber reactive polyazo dyes containing two urea groups |
| JP2007291246A (en) * | 2006-04-25 | 2007-11-08 | Mitsubishi Chemicals Corp | Azo dye, composition for anisotropic dye film having the dye, anisotropic dye film, and polarizing element |
-
2019
- 2019-08-29 CN CN201910807391.0A patent/CN110628237A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2904124A1 (en) * | 1979-02-03 | 1980-08-14 | Hoechst Ag | WATER-SOLUBLE, FIBER-REACTIVE DISAZO DYES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE FOR COLORING AND PRINTING FIBER MATERIALS CONTAINING HYDROXY GROUPS AND CARBONAMID GROUPS |
| US5831039A (en) * | 1997-04-15 | 1998-11-03 | Dystar Textilfarben Gmbh & Co. Deutschland Kg | Fiber reactive polyazo dyes containing two urea groups |
| JP2007291246A (en) * | 2006-04-25 | 2007-11-08 | Mitsubishi Chemicals Corp | Azo dye, composition for anisotropic dye film having the dye, anisotropic dye film, and polarizing element |
Non-Patent Citations (2)
| Title |
|---|
| DONG HYUN SONG ET AL.: "Orientation Behavior of Dichroic Azo Dyes in Stretched Poly(vinyl alcohol) Films", 《MOLECULAR CRYSTALS AND LIQUID CRYSTALS》 * |
| 王德虎 等: "易洗涤活性染料轧染染色性能研究", 《印染助剂》 * |
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Application publication date: 20191231 |